TWI460263B - Protective film forming liquid - Google Patents

Description

Protective film forming liquid

The present invention relates to a cleaning technique for a substrate (wafer) which is intended to improve the manufacturing yield of a circuit patterning element which is particularly fine and has a relatively high aspect ratio in the manufacture of a semiconductor element or the like. In particular, the present invention relates to a water repellent protective film forming chemical liquid or the like which is intended to improve a washing step in which a concave-convex pattern of a wafer having a fine uneven pattern on the surface is easily collapsed.

For semiconductor components for networking or digital home appliances, further high performance, high functionality, or low power consumption are required. Therefore, the miniaturization of the circuit pattern is accompanied by miniaturization of the particle size which causes a decrease in the manufacturing yield. As a result, a cleaning step for removing contaminants such as fine particles is often used, and as a result, the washing step accounts for 3 to 40% of the entire semiconductor manufacturing step.

On the other hand, when the conventionally washed with a mixed detergent of ammonia is used, the damage of the alkaline to the wafer becomes a problem as the circuit pattern is miniaturized. Therefore, it has been developed to replace with less damaging such as dilute hydrofluoric acid detergent.

Thereby, although the problem of damage to the wafer by the cleaning is improved, the problem caused by the increase in the aspect ratio of the pattern tends to become apparent as the semiconductor element is miniaturized. That is, after washing or rinsing, when the gas-liquid interface passes through the pattern, the pattern collapses, and the yield is greatly reduced.

This pattern collapse occurs when the wafer is lifted from the cleaning solution or the rinsing liquid. The reason is considered to be: the higher and upper part of the pattern and the lower part A difference in the height of the residual liquid is formed between the points, whereby a capillary force acting on the pattern causes a difference.

Therefore, when the capillary force is reduced, it is expected that the difference in capillary force caused by the difference in the height of the residual liquid is lowered, and the pattern collapse is eliminated. The magnitude of the capillary force is the absolute value of P obtained by the following formula. If γ or cos θ is decreased according to the formula, it is expected that the capillary force can be lowered.

P = 2 × γ × coSθ / S (γ: surface tension, θ: contact angle, S: pattern size)

Patent Document 1 discloses a technique for reducing γ to suppress pattern collapse, and discloses a technique in which a cleaning liquid is replaced with water to 2-propanol before passing through a pattern at a gas-liquid interface. However, this method is effective for preventing pattern collapse. On the other hand, the usual contact angle of a solvent such as 2-propanol having a small γ is small, and as a result, cos θ tends to increase. Therefore, there is a limit that the aspect ratio of the pattern that can be matched is 5 or less.

Further, in Patent Document 2, as a method of reducing cos θ and suppressing pattern collapse, a technique in which a resist pattern is targeted is disclosed. This method is a method in which the contact angle is set to be around 90°, whereby the cos θ is close to 0 and the capillary force is lowered to the limit, thereby suppressing pattern collapse. However, the disclosed technology targets the resist pattern and modifies the resist itself, and may eventually be removed together with the resist, so that it is not necessary to envisage the removal of the treatment agent after drying, and thus it is impossible to Used for this purpose.

Further, Patent Document 3 discloses that a surface of a wafer having a pattern of irregularities formed by a film containing ruthenium is surface-modified by oxidation or the like, and a water-soluble surfactant or a decane coupling agent is used to form water repellency on the surface. protection Membrane, a method of cleaning the capillary force and preventing the pattern from collapsing. However, the water repellent used in the above has a case where the water repellency imparting effect is insufficient.

Further, as a method of preventing pattern collapse of a semiconductor element, use of a critical fluid, use of liquid nitrogen, or the like has been proposed. However, any of the methods has a certain effect, but the yield is poorer than the previous washing process, and thus it is difficult to apply to the mass production step.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-198958

Patent Document 2: Japanese Patent Laid-Open No. Hei 5-299336

Patent Document 3: Japanese Patent No. 4403202

When manufacturing a semiconductor element, the surface of the wafer is set to have a surface having a fine uneven pattern. An object of the present invention is to provide a chemical solution for forming a protective film which uses a wafer having a fine uneven pattern on its surface and at least a part of which has a ruthenium element (hereinafter referred to as "矽 wafer" or only "crystal" In the manufacturing method of the circle"), a water repellent protective film is formed on the surface of the concave-convex pattern of the wafer, and the washing step which is liable to cause pattern collapse is improved without impairing the yield.

In the surface of the concave-convex pattern of the wafer of the present invention, a protective liquid for forming a protective film for water repellent protective film (hereinafter referred to as "chemical liquid for forming a protective film" or simply "chemical liquid") is formed, which is characterized in that it is washed. When the wafer having a fine concavo-convex pattern on the clean surface and at least a part of the concavo-convex pattern contains a germanium element, the water repellent protection is formed on at least the concave surface of the concavo-convex pattern. A chemical solution of a film (hereinafter referred to as a "water repellency protective film" or only a "protective film"), and an oxime compound A represented by the following formula [1] and an acid which supplies a proton to the hydrazine compound A Or/and the self-purifying compound A receives an acid of an electron, and the total amount of water in the chemical solution is 1000 ppm by mass or less based on the total amount of the chemical solution.

R ¹ _a Si(H) _b (X) _4-ab [1] (In the formula [1], R ^{1 is} independently from each other and is selected from a hydrocarbon group having a carbon number of 1 to 18; a group and at least one group of a monovalent organic group having a fluoroalkyl chain having 1 to 8 carbon atoms, wherein X is independently selected from a halogen group, and an element bonded to the Si element is an oxygen or a nitrogen. At least one of a group and a nitrile group, a is an integer of 1 to 3, b is an integer of 0 to 2, and a total of a and b is 3 or less).

The above general formula [1] The R & lt reduce ^a surface energy of the article to reduce water or other liquid between the article surface (interface) of interactions such as hydrogen bonding, intermolecular force and the like. In particular, the effect of reducing the interaction with water is large, but it also has the effect of reducing the interaction between a mixture of water and a liquid other than water, or a liquid other than water. Thereby, the contact angle of the liquid with the surface of the article can be enlarged.

The protective film is formed by chemically bonding the X element of the above formula [1] to the Si element of the germanium wafer. Therefore, when the cleaning liquid is removed from the concave portion of the silicon wafer, that is, when the drying is performed, the protective film is formed on the surface of the concave portion. Therefore, the capillary force on the surface of the concave portion is lowered, and pattern collapse is less likely to occur. Further, the above protective film can be removed by the subsequent steps.

The acid acts by supplying a proton to the ruthenium compound A or accepting electrons from the ruthenium compound A, thereby functioning as a catalyst for promoting the reaction of the ruthenium compound A with the Si element of the ruthenium wafer. It is considered that the acid acts as shown in the mechanism shown below. Further, in the figure, the acid meter is referred to as "L". The acid is present in the above-mentioned chemical solution, whereby a protective film can be formed in a short time. Further, the above acid may also form part of the protective film.

When the amount of water is more than the above-mentioned acid, the acid is supplied to the water or the electrons are received from the water. Therefore, the action as the catalyst is liable to lower, and it is difficult to form the protective film. Therefore, the total amount of water in the chemical solution is preferably 5,000 ppm by mass or less based on the total amount of the chemical solution. When the amount of water exceeds 5,000 ppm by mass, it is difficult to form the above protective film in a short time. Therefore, the total amount of the above-mentioned water is preferably as small as possible, and particularly preferably 1000 ppm by mass or less, and further preferably 500 ppm by mass or less. Further, when the amount of water is large, the storage stability of the chemical liquid is liable to lower, so that the amount of water is preferably as small as possible, and is preferably 200 ppm by mass or less. It is preferably 100 ppm by mass or less. Further, the total amount of the above water may be 0.1 mass ppm or more. Further, in the case of the raw material, the content of the acid water is preferably as small as possible, and the content of water in the raw material is preferably 35% by mass or less, particularly preferably 10% by mass or less, and further preferably 5 The mass% or less is more preferably 1% by mass or less. Further, the content of the acid water may be 0.001% by mass or more.

Further, the hydrazine compound A represented by the above formula [1] is preferably an alkoxy decane represented by the following formula [2].

[Formula ^{_{3] R 2 c Si (H}} ) d (OR 3) 4-cd [2] ( in the formula [2], R ² are each independently selected from a hydrocarbon group having a carbon number of 1 to 18 monovalent one An organic group and at least one group of a monovalent organic group having a fluoroalkyl chain having 1 to 8 carbon atoms, and each of R ^{3 is} independently selected from a part or all of hydrogen atoms, and the number of carbon atoms which may be substituted by a fluorine element is 1~ And a hydrocarbon group represented by R ³ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group. c is an integer of 1 to 3, and d is 0 to 2 The integer, the total of c and d is 3 or less).

Further, the alkoxydecane and the acid contained in the above chemical solution can also be obtained by a reaction. For example, it can also be obtained by reacting hydrazine compound B with an alcohol as shown in the following formula [3].

R ⁴ _e Si(H) _f (Y) _4-ef +(4-ef)R ⁵ -OH → R ⁴ _e Si(H) _f (OR ⁵ ) _4-ef +(4-ef) HY [3] (In the formula [3], R ⁴ _e Si(H) _f (Y) _4-ef represents an anthracene compound B, R ⁵ -OH represents an alcohol, and R ⁴ _e Si(H) _f (OR ⁵ ) _4-ef represents an alkoxydecane obtained by the reaction, and HY represents an acid; and R ^{4 is} independently selected from a hydrocarbon group having a carbon number of 1 to 18 and a fluorine having a carbon number of 1 to 8. At least one group of the monovalent organic groups of the alkyl chain, and R ⁵ are each independently at least one selected from the group consisting of a part or all of hydrogen elements which may be substituted by a fluorine element and having a carbon number of 1 to 18 one-valent hydrocarbon groups. The hydrocarbon group represented by R ⁵ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group. e is an integer of 1 to 3, f is an integer of 0 to 2, and a total of e and f is 3 or less. Further, Y is independently selected from the group consisting of a halogen group, -OS(O ₂ )-R ⁶ and -OC(O)-R ⁶ (wherein R ⁶ is a part or all of hydrogen elements which may be substituted by a fluorine element to have a carbon number of 1~ At least one of the hydrocarbon groups of 8).

Further, the chemical solution for forming a protective film of the present invention may further comprise a ruthenium compound C represented by the following formula [4] and a base having a water content of 35% by mass or less, and the total amount of water in the above chemical solution is relative to the total amount of the liquid solution. The amount is 1000 ppm by mass or less.

R ⁷ _g Si(H) _h (CH ₃ ) _w (Z) _4-ghw [4] (In the formula [4], R ^{7 is} independently selected from the group consisting of a carbon number of 2 to 18 a monovalent organic group of a hydrocarbon group and at least one group of a monovalent organic group containing a fluoroalkyl chain having 2 to 8 carbon atoms, each independently selected from a halogen group, and an element bonded to the Si element is oxygen At least one of the monovalent organic groups, g is an integer of 0 to 3, h is an integer of 0 to 2, w is an integer of 0 to 2, and the total of g and h is 1 to 3, and the total of g and w is 1~3, the total of g, h and w is 1~3).

R ⁷ and CH _{3 of the} above formula [4] lower the surface energy of the article and reduce the interaction (interfacial) between water or other liquid and the surface of the article (such as hydrogen bonding, intermolecular force, and the like). In particular, the effect of reducing the interaction with water is large, but it also has the effect of reducing the interaction between a mixture of water and a liquid other than water, or a liquid other than water. Thereby, the contact angle of the liquid with the surface of the article can be enlarged.

The protective film is formed by chemically bonding the Z element of the above formula [4] with the Si element of the germanium wafer. Therefore, when the cleaning liquid is removed from the concave portion of the silicon wafer, that is, when the drying is performed, the protective film is formed on the surface of the concave portion. Therefore, the capillary force on the surface of the concave portion is lowered, and pattern collapse is less likely to occur. Further, the above protective film can be removed by the subsequent steps.

The above-mentioned base functions as a catalyst for promoting the reaction of the above-mentioned cerium compound C with the Si element of the cerium wafer. The base is present in the above-mentioned chemical liquid, whereby a protective film can be formed in a short time. Further, the above base may also form part of the protective film.

When the base contains water, the amount of water contained in the above-mentioned chemical solution increases, and it is difficult to form the protective film. Therefore, the water content of the alkali is preferably as small as possible, and the water content is preferably 35% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less. . Further, the water content of the alkali may be 0.001% by mass or more.

Further, the oxime compound C represented by the above formula [4] is preferably an alkoxy decane represented by the following formula [5].

R ⁸ _i Si(H) _j (CH ₃ ) _k (OR ⁹ ) _4-ijk [5] (In the formula [5], R ^{8 is} independently selected from the group consisting of a carbon number of 2 to 18 a hydrocarbon-based one-valent organic group and at least one group of a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, and R ⁹ are each independently selected from a part or all of hydrogen elements and may be substituted by a fluorine element. The carbon number is at least one of a monovalent hydrocarbon group of 1 to 18. Further, the hydrocarbon group represented by R ⁹ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group. i is an integer of 0 to 3, j is an integer from 0 to 2, k is an integer from 0 to 2, the total of i and j is 1 to 3, the total of i and k is 1 to 3, and the total of i, j and k is 1 to 3).

Further, the alkoxysilane and the base contained in the above chemical solution can also be obtained by a reaction. For example, it can also be obtained by reacting the hydrazine compound D with an alcohol as shown in the following formula [6] or formula [7].

R ¹⁰ _p Si(H) _q (CH ₃ ) _r (W) _4-pqr +(4-pqr)R ¹¹ -OH → R ¹⁰ _p Si(H) _q (CH ₃ ) _r (OR ¹¹ ) _4-pqr +(4-pqr)HW [6] [R ¹² _s (CH ₃ ) _t (H) _u Si] _v NR ¹³ _3-v +v R ¹⁴ -OH → v R ¹² _s (CH ₃ ) _t (H) _u SiOR ¹⁴ +N(H)) _v (R ¹³ ) _3-v [7] (in the formula [6], R ¹⁰ _p Si(H) _q (CH ₃ ) _r (W) _{4- pqr} silicon compound represented by D, R ¹¹ -OH represents an _{^{alcohol, R 10 p Si (H)}} q (CH 3) r (OR 11) 4-pqr represents alkoxy Silane obtained by the reaction of, HW represents an alkali. In addition, In the formula [7], [R ¹² _s (CH ₃ ) _t (H) _u Si] _v NR ¹³ _3-v represents an indole compound D, R ¹⁴ -OH represents an alcohol, R ¹² _s (CH ₃ ) _t (H) _u SiOR ¹⁴ represents an alkoxydecane obtained by the reaction, and N(H) _v (R ¹³ ) _3-v represents a base. R ^{10 is} independently from each other and is selected from a hydrocarbon group having a carbon number of 2 to 18. An organic group and at least one group of a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, and R ¹¹ are each independently selected from a part or all of hydrogen atoms, and the number of carbon atoms which may be substituted by a fluorine element is 1~ At least one group of 18-valent hydrocarbon groups. Further, the hydrocarbon group represented by R ¹¹ may further comprise one of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group. And R ¹² are each independently at least one selected from the group consisting of a monovalent organic group having a hydrocarbon group having 2 to 18 carbon atoms and a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, R ^{13 is} independently selected from at least one group selected from the group consisting of a monovalent organic group having 1 to 8 carbon atoms and hydrogen, and each of R ^{14 is} independently selected from a part or all of hydrogen. The number of carbon atoms which may be substituted by fluorine is 1~ 18 of at least one monovalent hydrocarbon group of one. Moreover, the hydrocarbon group represented by R ¹⁴ may contain a carbonyl group, an ether bond, an ester bond, one or more of hydroxy .p of integers of 0 to 3, q is 0 to 2 The integer, r is an integer from 0 to 2, the total of p and q is 1 to 3, the sum of p and r is 1 to 3, the total of p, q and r is 1 to 3, and s is an integer of 0 to 3. , t is an integer from 0 to 2, u is an integer from 0 to 2, and the total of s, t, and u is 3, and v is an integer from 1 to 3. Further, W is independently selected from the group consisting of an amine group and a dialkyl group. At least one of an amino group and an isocyanate group).

Further, when the particles are measured by the light scattering type liquid particle detector in the liquid phase in the chemical solution, the number of particles larger than 0.5 μm is preferably 100 or less per 1 mL of the chemical solution. If the number of particles larger than 0.5 μm is more than 100 per 1 mL of the chemical solution, the pattern damage caused by the particles is caused, and the component yield is lowered and the reliability is lowered, which is not preferable. Moreover, when the number of particles larger than 0.5 μm is 100 or less per 1 mL of the chemical liquid, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Further, the number of particles larger than 0.5 μm may be one or more per 1 mL of the chemical solution. Further, the measurement of the particles in the liquid phase in the chemical solution of the present invention is measured by a commercially available measuring device for measuring the particle size in a laser light scattering type liquid using a laser as a light source, and the particle diameter of the particle means PSL. (Polystyrene Latex, made of polystyrene Latex) The standard particle reference light scattering approximate diameter.

Further, it is preferable that the content of the metal impurities of each of elements of Na, Mg, K, Ca, Mn, Fe, and Cu in the chemical solution is 100 mass ppb or less with respect to the total amount of the chemical liquid. The metal impurities of the respective elements are all in the form of metal fine particles, ions, colloids, complexes, oxides, or nitrides, and are present in the chemical solution regardless of whether they are dissolved or dissolved. When the content of the metal impurities exceeds 100 mass ppb with respect to the total amount of the chemical liquid, the junction leakage current of the element increases, which causes a decrease in the component yield and a decrease in reliability, which is not preferable. In addition, when the content of the metal impurities is 100 mass ppb or less with respect to the total amount of the chemical liquid, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Further, the content of the metal impurities may be 0.01 mass ppb or more with respect to the total amount of the chemical liquid, respectively.

The protective film forming chemical solution of the present invention is used in a washing step of forming a wafer having a concave-convex pattern, and the cleaning liquid is replaced with the chemical liquid. Further, the above-mentioned substituted chemical solution may be replaced with another washing liquid.

When the cleaning liquid is replaced with the chemical solution forming liquid, and the chemical liquid is held on at least the concave portion surface of the concave-convex pattern, the protective film is formed on at least the concave portion surface of the concave-convex pattern. The protective film of the present invention does not have to be formed continuously, and it is not necessary to form it uniformly, but it is more preferably continuously and uniformly formed in order to impart more excellent water repellency.

In the present invention, the water repellent protective film for a wafer refers to a film which is formed on the surface of the wafer to reduce the wettability of the surface of the wafer, that is, a film which imparts water repellency. In the present invention, the term "water repellency" means reducing the surface of the article. The surface energy reduces the interaction between water or other liquids (the interface) between the surface of the article, such as hydrogen bonding, intermolecular forces, and the like. In particular, the effect of reducing the interaction with water is large, but it also has the effect of reducing the interaction between a mixture of water and a liquid other than water, or a liquid other than water. By the decrease in the interaction, the contact angle of the liquid with the surface of the article can be enlarged.

In the present invention, when the cleaning liquid is removed from the concave portion, that is, when the drying is performed, the protective film is formed on at least the surface of the concave portion of the concave-convex pattern. Therefore, the capillary force on the surface of the concave portion is lowered, and pattern collapse is less likely to occur. Further, the protective film may be at least selected from the group consisting of a process of irradiating a surface of a wafer with light, a process of heating a wafer, a process of exposing the wafer to ozone, and a process of irradiating the surface of the wafer with plasma. A treatment to remove.

Since the protective film formed by the chemical solution for forming a protective film of the present invention is excellent in water repellency, the capillary force on the surface of the concave-convex pattern of the wafer is lowered, and the pattern collapse preventing effect is further exhibited. When this chemical liquid is used, the washing step in the manufacturing method of the wafer having the fine uneven pattern on the surface is not required to be reduced. Therefore, the method for producing a wafer having a fine uneven pattern on the surface by using the protective film forming chemical solution of the present invention has high productivity.

The chemical solution for forming a protective film of the present invention can also cope with a concave-convex pattern having an aspect ratio of, for example, 7 or more which is expected to be improved in the future, and can reduce the cost of production of a semiconductor element having a higher density. Further, it is possible to cope with the failure of the prior art device, and the result can be applied to the manufacture of various semiconductor elements.

A preferred cleaning method using a wafer having a fine concavo-convex pattern on the surface of the protective film forming solution of the present invention and having at least a portion of the concavo-convex pattern containing germanium element includes the following steps: (step 1) setting the surface of the wafer to have After the surface of the fine concavo-convex pattern is applied, the aqueous cleaning solution is supplied to the surface to hold the aqueous cleaning solution on at least the concave portion of the concave-convex pattern; (Step 2) the aqueous cleaning solution held on the surface of at least the concave portion of the concave-convex pattern is (Replacement 3) replacing the cleaning solution A different from the aqueous cleaning solution; (Step 3) replacing the cleaning liquid A with the protective film forming chemical solution, and holding the chemical solution on at least the concave portion surface of the concave-convex pattern; (Step 4) The liquid is removed from the surface of the relief pattern by drying; and (step 5) the protective film is removed.

Further, after the step of holding the protective film forming chemical solution on at least the concave portion surface of the concave-convex pattern (step 3), the chemical liquid held on the surface of at least the concave portion of the concave-convex pattern may be replaced with the chemical liquid. After the different cleaning liquid B, the process proceeds to a step of removing the liquid from the surface of the concave-convex pattern by drying (step 4). Further, after the water-based cleaning liquid containing the aqueous solution is held on the surface of at least the concave portion of the concave-convex pattern by replacing the cleaning liquid B, the step of transitioning to removing the liquid from the surface of the concave-convex pattern by drying may be performed (step 4). ). In the case where the protective film forming chemical solution is replaced with a water-based cleaning liquid, the replacement by the cleaning liquid B may be omitted.

In the present invention, the cleaning method of the wafer is not particularly limited as long as the chemical liquid or the cleaning liquid can be held on at least the surface of the concave portion of the concave-convex pattern of the wafer. As a method of cleaning the wafer, one can hold the crystal substantially horizontally. a circular piece that rotates, a one-piece method represented by a rotary washing in which a wafer is washed in the vicinity of a center of rotation, and a wafer is washed in a cleaning tank, and a plurality of wafers are immersed in a cleaning tank and washed. Secondary mode. In addition, the form of the chemical liquid or the cleaning liquid when the chemical liquid or the cleaning liquid is supplied to the surface of at least the concave portion of the concave-convex pattern of the wafer is not particularly limited as long as it is liquid when held on the surface of the concave portion, for example, for example, There are liquids, vapors, etc.

The chemical solution for forming a protective film contains the hydrazine compound A represented by the following formula [1] or the hydrazine compound C represented by the following formula [4].

R ¹ _a Si(H) _b (X) _4-ab [1] R ⁷ _g Si(H) _h (CH ₃ ) _w (Z) _4-ghw [4] (in formula [1] And R ¹ are each independently selected from at least one selected from the group consisting of a monovalent organic group having a hydrocarbon group having 1 to 18 carbon atoms and a monovalent organic group having a fluoroalkyl chain having 1 to 8 carbon atoms, and X respectively Independently selected from a halogen group, the element bonded to the Si element is at least one of an oxygen or nitrogen monovalent organic group and a nitrile group, a is an integer of 1 to 3, and b is an integer of 0 to 2, a and The total of b is 3 or less. Further, in the formula [4], R ^{7 is} each independently selected from a monovalent organic group having a hydrocarbon group having 2 to 18 carbon atoms and a fluoroalkyl group having 2 to 8 carbon atoms. At least one group of one of the chain organic groups, Z is independently from each other, and is selected from a halogen group, and the element bonded to the Si element is at least one group of one of the oxygen organic groups, and g is an integer of 0 to 3. h is an integer of 0 to 2, w is an integer of 0 to 2, the total of g and h is 1 to 3, the total of g and w is 1 to 3, and the total of g, h, and w is 1 to 3).

In the above formulas [1] and [4], examples of the halogen group of X and Z include a chlorine group, a bromine group and the like. Further, the element bonded to the Si element is oxygen or nitrogen. The organic group includes not only hydrogen, carbon, nitrogen, and oxygen but also lanthanum, sulfur, halogen, and the like. Examples of the one-valent organic group in which the element bonded to the Si element is nitrogen are an isocyanate group, an amine group, a dialkylamino group, an isothiocyanate group, an azide group, an ethenyl group, and -N ( CH ₃ )C(O)CH ₃ , -N(CH ₃ )C(O)CF ₃ , -N=C(CH ₃ )OSi(CH ₃ ) ₃ , -N=C(CF ₃ )OSi(CH _{3 3} , -NHC(O)-OSi(CH ₃ ) ₃ , -NHC(O)-NH-Si(CH ₃ ) ₃ , imidazole ring (the following formula [8]), Oxazolone ring (the following formula [9]), A porphyrin ring (the following formula [10]), -NH-C(O)-Si(CH ₃ ) ₃ , -N(H) _2-α (Si(H) _β R ¹ _3-β ) _α (α is 1 Or 2, β is an integer of 0 to 2, etc., and the element bonded to the Si element is a one-valent organic group of oxygen, and is bonded to the Si element on Si-OC or Si-OS, as Si- Examples of the OC bond are alkoxy, -OC(CH ₃ )=CHC(O)CH ₃ , -OC(CH ₃ )=N-Si(CH ₃ ) ₃ , -OC(CF ₃ )= N-Si(CH ₃ ) ₃ , -OC(O)-R ¹⁵ (R ¹⁵ is a hydrocarbon group in which some or all hydrogen elements may be substituted by a fluorine element and has a carbon number of 1 to 8), etc., as a bond on Si-OS Examples of the group include -OS(O ₂ )-R ¹⁶ (wherein R ¹⁶ is a hydrocarbon group in which a part or all of the hydrogen element may be substituted by a fluorine element and has 1 to 8 carbon atoms). Such an antimony compound A or C is rapidly reacted with X and Z as the reactive sites on the surface of the concavo-convex pattern of the crucible wafer, i.e., a decyl alcohol group, and the hydrazine compound A or C is bonded to the oxime via a decane bond. The Si element of the wafer is chemically bonded, whereby the surface of the wafer can be covered by the hydrophobic R ¹ group or the R ⁷ group, so that the capillary force of the concave surface of the wafer can be reduced in a short time.

[Chemistry 9]

In addition, when the X amount of the hydrazine compound A represented by 4-ab in the above formula [1] or the Z number of the hydrazine compound C represented by 4-ghw in the above formula [4] is 1, it is homogeneously It is more preferable to form the above protective film.

Further, if R ¹ in the above formula [1] is independently selected from C _m H _2m+1 (m=1 to 18) and C _n F _2n+1 CH ₂ CH ₂ (n=1 to 8), respectively. When at least one of the groups forms a protective film on the surface of the uneven pattern, the wettability of the surface can be further reduced, that is, the surface can be more excellent in water repellency, which is more preferable. Further, when m is 1 to 8 and n is 1 to 6, a protective film can be formed on the surface of the uneven pattern in a short time, which is more preferable.

The hydrazine compound A represented by the above formula [1] is preferably an alkoxy decane represented by the following formula [2].

R ² _c Si(H) _d (OR ³ ) _4-cd [2] (In the formula [2], R ^{2 is} independently from each other and is selected from a hydrocarbon group having a carbon number of 1 to 18 An organic group and at least one group of a monovalent organic group having a fluoroalkyl chain having 1 to 8 carbon atoms, and each of R ^{3 is} independently selected from a part or all of hydrogen atoms, and the number of carbon atoms which may be substituted by a fluorine element is 1~ And a hydrocarbon group represented by R ³ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group. c is an integer of 1 to 3, and d is 0 to 2 The integer, the total of c and d is 3 or less).

Further, if R ⁷ in the above formula [4] is independently selected from C _m H _2m+1 (m=2 to 18) and C _n F _2n+1 CH ₂ CH ₂ (n=2 to 8), respectively. When at least one of the groups forms a protective film on the surface of the uneven pattern, the wettability of the surface can be further reduced, that is, the surface can be more excellent in water repellency, which is more preferable. Further, when m is 2 to 8 and n is 2 to 6, a protective film can be formed on the surface of the uneven pattern in a short time, which is more preferable.

The hydrazine compound C represented by the above formula [4] is preferably an alkoxy decane represented by the following formula [5].

R ⁸ _i Si(H) _j (CH ₃ ) _k (OR ⁹ ) _4-ijk [5] (In the formula [5], R ^{8 is} independently selected from the group consisting of a carbon number of 2 to 18 a hydrocarbon-based one-valent organic group and at least one group of a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, and R ⁹ are each independently selected from a part or all of hydrogen elements and may be substituted by a fluorine element. The carbon number is at least one of a monovalent hydrocarbon group of 1 to 18. Further, the hydrocarbon group represented by R ⁹ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group. i is an integer of 0 to 3, j is an integer from 0 to 2, k is an integer from 0 to 2, the total of i and j is 1 to 3, the total of i and k is 1 to 3, and the total of i, j and k is 1 to 3).

Examples of the alkoxydecane include CH ₃ Si(OCH ₃ ) ₃ , C ₂ H ₅ Si(OCH ₃ ) ₃ , C ₃ H ₇ Si(OCH ₃ ) ₃ , and C ₄ H ₉ Si (OCH _{3 ). 3} , C ₅ H ₁₁ Si(OCH ₃ ) ₃ , C ₆ H ₁₃ Si(OCH ₃ ) ₃ , C ₇ H ₁₅ Si(OCH ₃ ) ₃ , C ₈ H ₁₇ Si(OCH ₃ ) ₃ , C ₉ H ₁₉ Si(OCH ₃ ) ₃ , C ₁₀ H ₂₁ Si(OCH ₃ ) ₃ , C ₁₁ H ₂₃ Si(OCH ₃ ) ₃ , C ₁₂ H ₂₅ Si(OCH ₃ ) ₃ , C ₁₃ H ₂₇ Si(OCH ₃ ) ₃ , C ₁₄ H ₂₉ Si(OCH ₃ ) ₃ , C ₁₅ H ₃₁ Si(OCH ₃ ) ₃ , C ₁₆ H ₃₃ Si(OCH ₃ ) ₃ , C ₁₇ H ₃₅ Si(OCH ₃ ) ₃ , C ₁₈ H ₃₇ Si(OCH ₃ ) ₃ , (CH ₃ ) ₂ Si(OCH ₃ ) ₂ , C ₂ H ₅ Si(CH ₃ )(OCH ₃ ) ₂ , (C ₂ H ₅ ) ₂ Si(OCH ₃ ) ₂ , C ₃ H ₇ Si(CH ₃ )(OCH ₃ ) ₂ , (C ₃ H ₇ ) ₂ Si(OCH ₃ ) ₂ , C ₄ H ₉ Si(CH ₃ )(OCH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Si (OCH ₃ ) ₂ , C ₅ H ₁₁ Si(CH ₃ )(OCH ₃ ) ₂ , C ₆ H ₁₃ Si(CH ₃ )(OCH ₃ ) ₂ , C ₇ H ₁₅ Si(CH ₃ )(OCH ₃ ) ₂ , C ₈ H ₁₇ Si(CH ₃ )(OCH ₃ ) ₂ , C ₉ H ₁₉ Si(CH ₃ )(OCH ₃ ) ₂ , C ₁₀ H ₂₁ Si(CH ₃ )(OCH ₃ ) ₂ , C ₁₁ H ₂₃ Si(CH ₃ )(OCH ₃ ) ₂ , C ₁₂ H ₂₅ Si(CH ₃ )(OCH ₃ ) ₂ , C ₁₃ H ₂₇ Si(CH ₃ )(OCH ₃ ) ₂ , C ₁₄ H ₂₉ Si(CH ₃ )(OCH ₃ ) ₂ , C ₁₅ H ₃₁ Si(CH ₃ )(OCH ₃ ) ₂ , C ₁₆ H ₃₃ Si(CH ₃ )(OCH ₃ ) ₂ , C ₁₇ H ₃₅ Si( CH ₃ )(OCH ₃ ) ₂ , C ₁₈ H ₃₇ Si(CH ₃ )(OCH ₃ ) ₂ , (CH ₃ ) ₃ SiOCH ₃ , C ₂ H ₅ Si(CH ₃ ) ₂ OCH ₃ , (C ₂ H _{5 2} Si(CH ₃ )OCH ₃ , (C ₂ H ₅ ) ₃ SiOCH ₃ , C ₃ H ₇ Si(CH ₃ ) ₂ OCH ₃ , (C ₃ H ₇ ) ₂ Si(CH ₃ )OCH ₃ , (C ₃ H ₇ ) ₃ SiOCH ₃ , C ₄ H ₉ Si(CH ₃ ) ₂ OCH ₃ , (C ₄ H ₉ ) ₃ SiOCH ₃ , C ₅ H ₁₁ Si(CH ₃ ) ₂ OCH ₃ , C ₆ H ₁₃ Si ( CH ₃ ) ₂ OCH ₃ , C ₇ H ₁₅ Si(CH ₃ ) ₂ OCH ₃ , C ₈ H ₁₇ Si(CH ₃ ) ₂ OCH ₃ , C ₉ H ₁₉ Si(CH ₃ ) ₂ OCH ₃ , C ₁₀ H ₂₁ Si(CH ₃ ) ₂ OCH ₃ , C ₁₁ H ₂₃ Si(CH ₃ ) ₂ OCH ₃ , C ₁₂ H ₂₅ Si(CH ₃ ) ₂ OCH ₃ , C ₁₃ H ₂₇ Si(CH ₃ ) ₂ OCH ₃ , C ₁₄ H ₂₉ Si(CH ₃ ) ₂ OCH ₃ , C ₁₅ H ₃₁ Si(CH ₃ ) ₂ OCH ₃ , C ₁₆ H ₃₃ Si(CH ₃ ) ₂ OCH ₃ , C ₁₇ H ₃₅ Si(CH ₃ ) ₂ OCH ₃ , C ₁₈ H ₃₇ Si(CH ₃ ) ₂ OCH ₃ , (CH ₃ ) ₂ Si(H)OCH ₃ , CH ₃ Si(H) ₂ OCH ₃ , (C ₂ H ₅ ) ₂ Si(H)OCH ₃ , C ₂ H ₅ Si(H) ₂ OCH ₃ , C ₂ H ₅ Si(CH ₃ )(H)OCH ₃ , (C ₃ H ₇ ) ₂ Si(H)OCH ₃ and other alkyl methoxy Base decane, or CF ₃ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )(OCH ₃ ) ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) (OCH ₃ ) ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ )(OCH ₃ ) ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ )(OCH ₃ ) ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ )(OCH ₃ ) ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ )(OCH ₃ ) ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si (CH ₃ )(OCH _{3 2} , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )(OCH ₃ ) ₂ , CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ OCH ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OCH ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ OCH ₃ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ OCH ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si (CH _{3 2} OCH ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ OCH ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OCH ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH _{3) 2 OCH 3, CF 3} CH 2 CH 2 Si (CH 3) (H) OCH 3 and the like ylmethoxy Silane fluoroalkyl, or The methyl moiety of the above-methoxy-methoxy-silane-substituted compound of the carbon atoms other than methyl group as one of the monovalent organic group having 1 to 18 addition.

Further, when R ^{3 of the} above formula [2] or R ⁹ of the above formula [5] is an alkyl group, a protective film can be formed on the surface of the uneven pattern in a short time, which is more preferable, and further, if it is a linear chain The alkyl group can further form the protective film in a short period of time, which is more preferable. Further, when the number of carbon atoms of the linear alkyl group is from 1 to 6, the protective film can be formed in a short time, which is more preferable.

As the acid in the above chemical solution, there are inorganic acids or organic acids. Examples of the inorganic acid having a small water content include hydrogen chloride, sulfuric acid, perchloric acid, phosphoric acid, etc., and examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and acetic acid. , trifluoroacetic acid, pentafluoropropionic acid, and the like.

Further, as the acid, a Lewis acid can also be used. The definition of Lewis acid is described, for example, in the "Chemical Chemistry Dictionary (Fifth Edition)". Examples of the Lewis acid include an acid anhydride, a boron compound, and a ruthenium compound. Examples of the acid anhydride include a part or all of a hydrogen atom such as trifluoromethanesulfonic anhydride, which may be substituted with a fluorine element or the like, an alkanesulfonic anhydride, acetic anhydride or trifluoroethane. A part or all of the hydrogen element such as an acid anhydride or pentafluoroacetic acid anhydride may be a carboxylic acid anhydride substituted with a fluorine element or the like. Examples of the boron compound include an alkyl borate ester, an aryl borate ester, and a tris(trifluoroethyl) group. Oxygen Boron, trialkoxyboroxane, trifluoroborate, etc., as an example of the ruthenium compound, a chlorodecane, a part or all of a hydrogen element may be substituted by a fluorine element or the like. The sulfonate, a part or all of the hydrogen element may be an alkyl sulfonyl carboxylate substituted with a fluorine element or the like. Further, in the case of using the above ruthenium compound, at least a part of the above protective film may be formed from the ruthenium compound.

Among these, in view of cleanliness, it is particularly preferred that the Bronsted acid, the acid anhydride, the chlorodecane, a part or all of the hydrogen element may be substituted with a fluorine atom or the like, an alkyl alkyl alkyl sulfonate, a part or All of the hydrogen elements may be an anthracene compound such as an alkyl mercaptoalkyl carboxylate substituted with a fluorine element or the like. Further, in the case of using the above ruthenium compound, at least a part of the above protective film may be formed from the ruthenium compound.

As the above base, there are ammonia, N, N, N', N'-tetramethylethylenediamine, triethylenediamine, dimethylaniline, alkylamine, pyridine, piperazine, N-alkyl Porphyrin, R ¹⁷ _x Si-A _4-x (R ^{17 is} independently of each other, some or all of the hydrogen elements may be substituted by fluorine or the like, and the carbon number is 1 to 18 one-valent hydrocarbon group, and A is bonded to the Si element. The element is nitrogen and may also contain a nitrogen-containing compound such as a fluorine element or a valence element organic group, and x is an integer of 1 to 3. In particular, ammonia or an alkylamine is preferred in view of the catalytic ability. Further, in the case of using R ¹⁷ _x Si-A _4-x , at least a part of the above protective film may be formed of R ¹⁷ _x Si-A _4-x .

The catalyst in the above-mentioned chemical solution is preferably an acid, and particularly preferably a strong acid of Brunsten acid or an anhydride thereof, or a part or all of a hydrogen atom substituted by a fluorine element or the like. Sulfonate, part or An alkyl decyl carboxylate in which all hydrogen elements are replaced by a fluorine element or the like.

In the above-mentioned chemical solution, the concentration of the acid or the base which acts as a catalyst is preferably 0.01 to 60% by mass based on 100% by mass of the total of the above-mentioned hydrazine compound A or the above hydrazine compound C. If the amount of addition is small, the catalyst effect is lowered, so that it is not good, and even if it is excessive, the catalyst effect is not improved, and conversely, there is a fear of eroding the surface of the wafer or remaining as an impurity on the wafer. Therefore, the catalyst concentration is particularly preferably 0.05 to 50% by mass based on 100% by mass of the total of the above ruthenium compound A or the above ruthenium compound C.

Further, in the above chemical solution, the hydrazine compound A and the acid or the hydrazine compound C and the base may be diluted with a solvent. When the total amount of the cerium compound A and the acid added or the total amount of the cerium compound C and the alkali added is 0.01 to 100% by mass based on 100% by mass of the total amount of the chemical liquid, the embossing is easy. It is preferable that at least the surface of the concave portion of the pattern uniformly forms a protective film. If it is less than 0.01% by mass, the protective effect of the uneven pattern tends to be insufficient. On the other hand, even if the sum of the addition amounts is increased, there is a fear of eroding the surface of the wafer or remaining as an impurity on the wafer. Further, it is preferably 0.05 to 50% by mass, more preferably 0.1 to 30% by mass.

As a solvent which may be used for dilution in the above-mentioned chemical liquid, for example, a hydrocarbon, an ester, an ether, a ketone, a halogen-containing solvent, an anthraquinone solvent, an alcohol, a derivative of a polyhydric alcohol, or the like may be preferably used. An organic solvent such as a nitrogen-containing compound solvent.

Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane; and examples of the ester include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetate. Etc.; as an example of the above ethers, there are diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, two An alkane or the like; as an example of the ketone, acetone, ethyl acetonide, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone or the like; as the above halogen-containing solvent For example, perfluorooctane, perfluorodecane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, etc., perfluorocarbon, 1,1,1,3,3-pentafluorobutane, octafluoro Hydrofluorocarbon such as cyclopentane, 2,3-dihydro decafluoropentane, Zeorora H (manufactured by ZEON, Japan), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, B Hydrofluoroethers such as perfluoroisobutyl ether, Asahiklin AE-3000 (made by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 (all manufactured by 3M), chlorocarbon such as tetrachloromethane, chloroform Hydrochlorofluorocarbon, chlorofluorocarbon such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2 , 3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, etc. Hydrochlorofluorocarbon, perfluoroether, perfluoropoly Examples of the above-mentioned anthraquinone-based solvent include dimethyl hydrazine and the like; and examples of the alcohol include methanol, ethanol, propanol, butanol, ethylene glycol, and 1,3-propanediol. As examples of the above derivatives of the polyol, there are diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate Ester, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ether, diethylene glycol diethyl ether, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, etc. As examples of the solvent of the nitrogen-containing compound, there are methotrexate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, diethylamine, and the like. Ethylamine, pyridine, and the like.

In addition, when the incombustibility is used in the above-mentioned organic solvent, the chemical solution for forming a protective film becomes incombustible or the flammable point rises, and the risk of the chemical liquid is lowered, which is preferable. The halogen-containing solvent is mostly incombustible, and the nonflammable halogen-containing solvent can be preferably used as a non-flammable organic solvent.

Even if a protic solvent is used as the diluent solvent in the chemical solution of the present invention, the effect of the above-mentioned hydrazine compound A or the above-mentioned acid or the effect of the above-mentioned hydrazine compound C or the above-mentioned base is hardly lowered. Therefore, a highly safe protic solvent, particularly an alcohol, can be used as a diluent solvent, so that the safety of the above-mentioned chemical liquid can be made high. The decane coupling agent or surfactant used in Patent Document 3 of the prior art has a tendency to decrease in activity due to mixing with a protic solvent, and it is difficult to obtain a desired water repellency or a tendency to decrease in yield, and thus, as shown in the present invention, The use of protic solvents is of great significance.

Further, when the chemical solution is supplied to the wafer while rotating the wafer, if the boiling point of the organic solvent is too low, the chemical liquid is easily dried before the chemical liquid is wetted and spread over the entire surface of the wafer. Therefore, it is not good. Further, when the boiling point is too high, the viscosity of the above-mentioned chemical liquid tends to be too high, which is not preferable. Therefore, the above organic solvent is preferably one having a boiling point of 70 to 220 °C. As such a solvent, in view of cost or solubility with other washing liquids (ease of substitution), among the above alcohols, 1-propanol and 2-propanol are preferred, and organic solvents other than the above alcohols are preferred. Diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene Alcohol diethyl ether, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol dimethyl ether, cyclohexanone.

Further, the total amount of water in the chemical solution is preferably 5,000 ppm by mass or less based on the total amount of the chemical solution. When the total amount of the water component exceeds 5,000 ppm by mass, the effect of the above-mentioned antimony compound A and the acid or the effect of the above-mentioned antimony compound C and the above-mentioned base is lowered, and it is difficult to form the protective film in a short time. Therefore, the total amount of the water content in the above-mentioned chemical liquid is preferably as small as possible, and particularly preferably 1000 ppm by mass or less, and further preferably 500 ppm by mass or less. In addition, when the amount of water is large, the storage stability of the chemical liquid is liable to lower. Therefore, the amount of water is preferably as small as possible, and is preferably 200 ppm by mass or less, and more preferably 100 ppm by mass or less. Further, the amount of water in the above chemical solution may be 0.1 mass ppm or more. Therefore, it is preferable that the hydrazine compound A contained in the above-mentioned chemical liquid, the above-mentioned hydrazine compound C, an acid, or a base, or the solvent contained in the above-mentioned chemical liquid, does not contain a large amount of water.

Further, when the particles are measured by the light scattering type liquid particle detector in the liquid phase in the chemical solution, the number of particles larger than 0.5 μm is preferably 100 or less per 1 mL of the chemical solution. If the number of particles larger than 0.5 μm is more than 100 per 1 mL of the chemical solution, the pattern damage caused by the particles is caused, and the component yield is lowered and the reliability is lowered, which is not preferable. Moreover, when the number of particles larger than 0.5 μm is 100 or less per 1 mL of the chemical liquid, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Therefore, the number of particles larger than 0.5 μm in the above-mentioned chemical liquid is preferably as small as possible per 1 mL of the chemical liquid, and particularly preferably 10 or less, more preferably 2 or less. Further, the number of particles larger than 0.5 μm may be one or more per 1 mL of the chemical solution.

Further, each of Na, Mg, K, Ca, Mn, Fe, and Cu in the above chemical solution The content of the metal impurities of the element is preferably 100 mass ppb or less with respect to the total amount of the chemical liquid, respectively. When the content of the metal impurities exceeds 100 mass ppb with respect to the total amount of the chemical liquid, the junction leakage current of the element increases, which causes a decrease in the component yield and a decrease in reliability, which is not preferable. In addition, when the content of the metal impurities is 100 mass ppb or less with respect to the total amount of the chemical liquid, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Therefore, the metal impurity content is preferably as small as possible, and particularly preferably 1 mass ppb or less, and more preferably 0.1 mass ppb or less. Further, the content of the metal impurities may be 0.01 mass ppb or more with respect to the total amount of the chemical liquid, respectively.

In the method for preparing a chemical solution for forming a protective film which is obtained by mixing the hydrazine compound A represented by the above formula [1] with an acid, it is preferably a mixture of the hydrazine compound A, the acid, and the mixed solution before mixing. At least one is purified. Further, when the chemical solution forming solution contains a solvent, the hydrazine compound A and the acid before the mixing may be in a solution state containing a solvent. In this case, the above-mentioned purification may also be carried out before the hydrazine compound A or a solution thereof. At least one of an acid or a solution thereof and a mixed liquid after mixing is used as a target.

Further, in the method for preparing a chemical solution for forming a protective film which is obtained by mixing the hydrazine compound C represented by the above formula [4] with an alkali, it is preferred to use at least at least a mixture of the hydrazine compound C, the alkali and the mixed solution. One is for purification. Further, when the chemical solution forming solution contains a solvent, the hydrazine compound C and the base before the mixing may be in a solution state containing a solvent. In this case, the above-mentioned purification may also be carried out before the hydrazine compound C or a solution thereof. At least one of a base or a solution thereof, and a mixed liquid after mixing is targeted.

The above purification uses removal of metal impurities such as an element such as Na, Mg, K, Ca, Mn, Fe, and Cu by an ion exchange resin or distillation, such as removal of water molecules by an adsorbent such as a molecular sieve or distillation, or the like. And at least one of removing the pollutants such as particles filtered by the filter. It is preferable to consider the reactivity of the protective film forming liquid or the cleanliness of the wafer, remove water molecules, remove metal impurities, and remove contaminants regardless of the order of removal.

In the method for preparing a protective film forming chemical solution which is obtained by mixing the hydrazine compound A represented by the above formula [1] with an acid, the acid and the solvent are preferably removed before being mixed with the hydrazine compound A. Moisture. Therefore, when the chemical solution for forming a protective film is prepared, it is preferred that the ruthenium compound A or the acid is not deactivated and the amount of moisture is easily reduced.

Further, in the method for preparing a chemical solution for forming a protective film which is obtained by mixing the hydrazine compound C represented by the above formula [4] with a base, the base and the solvent are preferably removed before being mixed with the hydrazine compound C. . Therefore, when the chemical solution for forming a protective film is prepared, it is preferred that the ruthenium compound C or the base is not deactivated and the amount of moisture is easily reduced.

The alkoxydecane and the acid contained in the above-mentioned chemical solution of the present invention can also be obtained by a reaction. For example, it can also be obtained by reacting hydrazine compound B with an alcohol as shown in the following formula [3].

R ⁴ _e Si(H) _f (Y) _4-cf +(4-ef)R ⁵ -OH → R ⁴ _e Si(H) _f (OR ⁵ ) _4-ef +(4-ef) HY [3] (In the formula [3], R ⁴ _e Si(H) _f (Y) _4-ef represents an anthracene compound B, R ⁵ -OH represents an alcohol, and R ⁴ _e Si(H) _f (OR ⁵ ) _4-ef represents an alkoxydecane obtained by the reaction, and HY represents an acid. R ^{4 is} independently selected from a hydrocarbon group having a carbon number of 1 to 18 and a fluorine having a carbon number of 1 to 8. At least one group of the monovalent organic groups of the alkyl chain, and R ⁵ are each independently at least one selected from the group consisting of a part or all of hydrogen elements which may be substituted by a fluorine element and having a carbon number of 1 to 18 one-valent hydrocarbon groups. The hydrocarbon group represented by R ⁵ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group. e is an integer of 1 to 3, f is an integer of 0 to 2, and a total of e and f is 3 or less. Further, Y is independently selected from the group consisting of a halogen group, -OS(O ₂ )-R ⁶ and -OC(O)-R ⁶ (wherein R ⁶ is a part or all of hydrogen elements which may be substituted by a fluorine element to have a carbon number of 1~ At least one of the hydrocarbon groups of 8).

Further, the alkoxysilane and the base contained in the above chemical solution can also be obtained by a reaction. For example, it can also be obtained by reacting the hydrazine compound D with an alcohol as shown in the following formula [6] or formula [7].

R ¹⁰ _p Si(H) _q (CH ₃ ) _r (W) _4-pqr +(4-pqr)R ¹¹ -OH → R ¹⁰ _p Si(H) _q (CH ₃ ) _r (OR ¹¹ ) _4-pqr +(4-pqr)HW [6] [R ¹² _s (CH ₃ ) _t (H) _u Si] _v NR ¹³ _3-v +v R ¹⁴ -OH → v R ¹² _s (CH ₃ ) _t (H) _u SiOR ¹⁴ +N(H) _v (R ¹³ ) _3-v [7] (in the formula [6], R ¹⁰ _p Si(H) _q (CH ₃ ) _r (W) _4-pqr Represents hydrazine compound D, R ¹¹ -OH represents an alcohol, R ¹⁰ _p Si(H) _q (CH ₃ ) _r (OR ¹¹ ) _4-pqr represents an alkoxy decane obtained by the reaction, and HW represents a base. In the formula [7], [R ¹² _s (CH ₃ ) _t (H) _u Si] _v NR ¹³ _3-v represents an anthracene compound D, R ¹⁴ -OH represents an alcohol, R ¹² _s (CH ₃ ) _t (H) _u SiOR ¹⁴ represents an alkoxydecane obtained by the reaction, and N(H) _v (R ¹³ ) _3-v represents a base. R ^{10 is} independently from each other and is selected from a hydrocarbon group having a carbon number of 2 to 18 a group and at least one group of a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, and each of R ^{11 is} independently selected from a part or all of hydrogen atoms and may be substituted by a fluorine element to have a carbon number of 1 to 18 At least one of the monovalent hydrocarbon groups. Further, the hydrocarbon group represented by R ¹¹ may further comprise one of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group. And R ¹² are each independently at least one selected from the group consisting of a monovalent organic group having a hydrocarbon group having 2 to 18 carbon atoms and a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, R ^{13 is} independently selected from at least one group selected from the group consisting of a monovalent organic group having 1 to 8 carbon atoms and hydrogen, and each of R ^{14 is} independently selected from a part or all of hydrogen. The number of carbon atoms which may be substituted by fluorine is 1~ 18 of at least one monovalent hydrocarbon group of one. Moreover, the hydrocarbon group represented by R ¹⁴ may contain a carbonyl group, an ether bond, an ester bond, one or more of hydroxy .p of integers of 0 to 3, q is 0 to 2 The integer, r is an integer from 0 to 2, the total of p and q is 1 to 3, the sum of p and r is 1 to 3, the total of p, q and r is 1 to 3, and s is an integer of 0 to 3. , t is an integer from 0 to 2, u is an integer from 0 to 2, and the total of s, t, and u is 3, and v is an integer from 1 to 3. Further, W is independently selected from the group consisting of an amine group and a dialkyl group. At least one of an amino group and an isocyanate group).

Further, the alcohol used in the above formulas [3], [6], and [7] is consumed by the reaction, but may remain in the obtained chemical solution. An excess amount of the alcohol is used as a raw material of the above formulas [3], [6], and [7], whereby the remaining alcohol component can also be used as a diluent solvent. The alkoxydecane obtained in the above formulas [3], [6], and [7] is difficult to reduce the activity of the acid or the base due to the remaining alcohol. Therefore, an alcohol having a higher safety can be used as a diluent solvent, so that the safety of the above-mentioned chemical liquid can be made high. The decane coupling agent or surfactant used in Patent Document 3 of the prior art has a tendency to decrease in activity due to mixing with a protic solvent, and it is difficult to obtain a desired water repellency or a tendency to decrease in yield. The use of alcohol solvents as indicated is significant. Further, as shown by the right side of the above formulas [3], [6], and [7], if a mixture of an alkoxydecane and an acid or a base is obtained, the above-mentioned hydrazine compound B and an alcohol or the above hydrazine may be used. A reaction other than the reaction of the compound D with an alcohol.

Examples of the ruthenium compound B include CH ₃ SiCl ₃ , C ₂ H ₅ SiCl ₃ , C ₃ H ₇ SiCl ₃ , C ₄ H ₉ SiCl ₃ , C ₅ H ₁₁ SiCl ₃ , C ₆ H ₁₃ SiCl ₃ , C ₇ H ₁₅ SiCl ₃ , C ₈ H ₁₇ SiCl ₃ , C ₉ H ₁₉ SiCl ₃ , C ₁₀ H ₂₁ SiCl ₃ , C ₁₁ H ₂₃ SiCl ₃ , C ₁₂ H ₂₅ SiCl ₃ , C ₁₃ H ₂₇ SiCl ₃ , C ₁₄ H ₂₉ SiCl ₃ , C ₁₅ H ₃₁ SiCl ₃ , C ₁₆ H ₃₃ SiCl ₃ , C ₁₇ H ₃₅ SiCl ₃ , C ₁₈ H ₃₇ SiCl ₃ , (CH ₃ ) ₂ SiCl ₂ , C ₂ H ₅ Si (CH ₃ ) Cl ₂ , (C ₂ H ₅ ) ₂ SiCl ₂ , C ₃ H ₇ Si(CH ₃ )Cl ₂ , (C ₃ H ₇ ) ₂ SiCl ₂ , C ₄ H ₉ Si(CH ₃ )Cl ₂ , (C ₄ H ₉ ) ₂ SiCl ₂ , C ₅ H ₁₁ Si(CH ₃ )Cl ₂ , C ₆ H ₁₃ Si(CH ₃ )Cl ₂ , C ₇ H ₁₅ Si(CH ₃ )Cl ₂ , C ₈ H ₁₇ Si( CH ₃ )Cl ₂ , C ₉ H ₁₉ Si(CH ₃ )Cl ₂ , C ₁₀ H ₂₁ Si(CH ₃ )Cl ₂ , C ₁₁ H ₂₃ Si(CH ₃ )Cl ₂ , C ₁₂ H ₂₅ Si(CH ₃ ) Cl ₂ , C ₁₃ H ₂₇ Si(CH ₃ )Cl ₂ , C ₁₄ H ₂₉ Si(CH ₃ )Cl ₂ , C ₁₅ H ₃₁ Si(CH ₃ )Cl ₂ , C ₁₆ H ₃₃ Si(CH ₃ )Cl ₂ , C ₁₇ H ₃₅ Si(CH ₃ )Cl ₂ , C ₁₈ H ₃₇ Si(CH ₃ )Cl ₂ , (CH ₃ ) ₃ SiCl, C ₂ H ₅ Si(CH ₃ ) ₂ Cl, (C ₂ H ₅ ) ₂ Si(CH ₃ )Cl, (C ₂ H ₅ ) ₃ SiCl, C ₃ H ₇ Si(CH ₃ ) ₂ Cl, (C ₃ H ₇ ) ₂ Si(CH ₃ )Cl, (C ₃ H ₇ ) ₃ SiCl, C ₄ H ₉ Si(CH ₃ ) ₂ Cl, (C ₄ H ₉ ) ₃ SiCl, C ₅ H ₁₁ Si(CH ₃ ) ₂ Cl, C ₆ H ₁₃ Si(CH ₃ ) ₂ Cl, C ₇ H ₁₅ Si(CH ₃ ) ₂ Cl, C ₈ H ₁₇ Si(CH ₃ ) ₂ Cl, C ₉ H ₁₉ Si(CH ₃ ) ₂ Cl, C ₁₀ H ₂₁ Si(CH ₃ ) ₂ Cl, C ₁₁ H ₂₃ Si(CH ₃ ) ₂ Cl, C ₁₂ H ₂₅ Si(CH ₃ ) ₂ Cl, C ₁₃ H ₂₇ Si(CH ₃ ) ₂ Cl, C ₁₄ H ₂₉ Si(CH ₃ ) ₂ Cl, C ₁₅ H ₃₁ Si(CH ₃ ) ₂ Cl, C ₁₆ H ₃₃ Si ( CH ₃ ) ₂ Cl, C ₁₇ H ₃₅ Si(CH ₃ ) ₂ Cl, C ₁₈ H ₃₇ Si(CH ₃ ) ₂ Cl, (CH ₃ ) ₂ Si(H)Cl, CH ₃ Si(H) ₂ Cl, (C ₂ H ₅ ) ₂ Si(H)Cl, C ₂ H ₅ Si(H) ₂ Cl, C ₂ H ₅ Si(CH ₃ )(H)Cl, (C ₃ H ₇ ) ₂ Si(H)Cl Or an alkyl chlorodecane, or CF ₃ CH ₂ CH ₂ SiCl ₃ , C ₂ F ₅ CH ₂ CH ₂ SiCl ₃ , C ₃ F ₇ CH ₂ CH ₂ SiCl ₃ , C ₄ F ₉ CH ₂ CH ₂ SiCl ₃ , C ₅ F ₁₁ CH ₂ CH ₂ SiCl ₃ , C ₆ F ₁₃ CH ₂ CH ₂ SiCl ₃ , C ₇ F ₁₅ CH ₂ CH ₂ SiCl ₃ , C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ CH ₂ CH ₂ Si (CH ₃ )Cl ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ )Cl ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ )Cl ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ )Cl ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ )Cl ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ )Cl ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ )Cl ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )Cl ₂ , CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ Cl, C ₂ F ₅ CH ₂ CH ₂ Si (CH _{3 2} Cl, C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ Cl, C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ Cl, C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ ) ₂ Cl, C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ Cl, C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ Cl, C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ Cl, Fluorinated alkyl chlorodecane such as CF ₃ CH ₂ CH ₂ Si(CH ₃ )(H)Cl or substituted with a chloro group of the above chlorodecane to a halogen group such as a bromo group, -OS(O ₂ )-R ⁶ and -OC (O) -R ⁶ (R ⁶ is a hydrogen elements may be partially or entirely substituted by fluorine element of carbon atoms of the hydrocarbon group having 1 to 8) were formed.

Examples of the ruthenium compound D include C ₂ H ₅ Si(NH ₂ ) ₃ , C ₃ H ₇ Si(NH ₂ ) ₃ , C ₄ H ₉ Si(NH ₂ ) ₃ , and C ₅ H ₁₁ Si (NH). ₂ ) ₃ , C ₆ H ₁₃ Si(NH ₂ ) ₃ , C ₇ H ₁₅ Si(NH ₂ ) ₃ , C ₈ H ₁₇ Si(NH ₂ ) ₃ , C ₉ H ₁₉ Si(NH ₂ ) ₃ , C ₁₀ H ₂₁ Si(NH ₂ ) ₃ , C ₁₁ H ₂₃ Si(NH ₂ ) ₃ , C ₁₂ H ₂₅ Si(NH ₂ ) ₃ , C ₁₃ H ₂₇ Si(NH ₂ ) ₃ , C ₁₄ H ₂₉ Si(NH _{2 3} , C ₁₅ H ₃₁ Si(NH ₂ ) ₃ , C ₁₆ H ₃₃ Si(NH ₂ ) ₃ , C ₁₇ H ₃₅ Si(NH ₂ ) ₃ , C ₁₈ H ₃₇ Si(NH ₂ ) ₃ , C ₂ H ₅ Si(CH ₃ )(NH ₂ ) ₂ , (C ₂ H ₅ ) ₂ Si(NH ₂ ) ₂ , C ₃ H ₇ Si(CH ₃ )(NH ₂ ) ₂ , (C ₃ H ₇ ) ₂ Si ( NH ₂ ) ₂ , C ₄ H ₉ Si(CH ₃ )(NH ₂ ) ₂ , (C ₄ H ₉ ) ₂ Si(NH ₂ ) ₂ , C ₅ H ₁₁ Si(CH ₃ )(NH ₂ ) ₂ , C ₆ H ₁₃ Si (CH ₃ )(NH ₂ ) ₂ , C ₇ H ₁₅ Si(CH ₃ )(NH ₂ ) ₂ , C ₈ H ₁₇ Si(CH ₃ )(NH ₂ ) ₂ , C ₉ H ₁₉ Si( CH ₃ )(NH ₂ ) ₂ , C ₁₀ H ₂₁ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₁ H ₂₃ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₂ H ₂₅ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₃ H ₂₇ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₄ H ₂₉ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₅ H ₃₁ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₆ H ₃₃ Si (CH ₃ (NH ₂ ) ₂ , C ₁₇ H ₃₅ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₈ H ₃₇ Si(CH ₃ )(NH ₂ ) ₂ , C ₂ H ₅ Si(CH ₃ ) ₂ NH ₂ , (C ₂ H ₅ ) ₂ Si(CH ₃ )NH ₂ , (C ₂ H ₅ ) ₃ SiNH ₂ , C ₃ H ₇ Si(CH ₃ ) ₂ NH ₂ , (C ₃ H ₇ ) ₂ Si(CH ₃ ) NH ₂ , (C ₃ H ₇ ) ₃ SiNH ₂ , C ₄ H ₉ Si(CH ₃ ) ₂ NH ₂ , (C ₄ H ₉ ) ₃ SiNH ₂ , C ₅ H ₁₁ Si(CH ₃ ) ₂ NH ₂ , C ₆ H ₁₃ Si(CH ₃ ) ₂ NH ₂ , C ₇ H ₁₅ Si(CH ₃ ) ₂ NH ₂ , C ₈ H ₁₇ Si(CH ₃ ) ₂ NH ₂ , C ₉ H ₁₉ Si(CH ₃ ) ₂ NH ₂ , C ₁₀ H ₂₁ Si(CH ₃ ) ₂ NH ₂ , C ₁₁ H ₂₃ Si(CH ₃ ) ₂ NH ₂ , C ₁₂ H ₂₅ Si(CH ₃ ) ₂ NH ₂ , C ₁₃ H ₂₇ Si(CH ₃ ) ₂ NH ₂ , C ₁₄ H ₂₉ Si(CH ₃ ) ₂ NH ₂ , C ₁₅ H ₃₁ Si(CH ₃ ) ₂ NH ₂ , C ₁₆ H ₃₃ Si(CH ₃ ) ₂ NH ₂ , C ₁₇ H ₃₅ Si (CH _{3 2} NH ₂ , C ₁₈ H ₃₇ Si(CH ₃ ) ₂ NH ₂ , (CH ₃ ) ₂ Si(H)NH ₂ , CH ₃ Si(H) ₂ NH ₂ , (C ₂ H ₅ ) ₂ Si(H NH ₂ , C ₂ H ₅ Si(H) ₂ NH ₂ , C ₂ H ₅ Si(CH ₃ )(H)NH ₂ , (C ₃ H ₇ ) ₂ Si(H)NH ₂ , CF ₃ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si (NH ₂ ) ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(NH _{2 3} , CF ₃ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) (NH ₂ ) ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )(NH _{2 2} , CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )(H An amine decane such as NH ₂ or a substituted alkyl group of the above amino decane to a dialkylamino group or an isocyanate group, or C ₂ H ₅ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ C ₂ H ₅ , C ₃ H ₇ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ C ₃ H ₇ , C ₄ H ₉ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ C ₄ H ₉ , C ₅ H ₁₁ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ C ₅ H ₁₁ , C ₆ H ₁₃ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ C ₆ H ₁₃ , C ₈ H ₁₇ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ C ₈ H ₁₇ , C ₆ H ₅ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ C ₆ H ₅ , {C ₂ H ₅ Si(CH ₃ ) ₂ } ₃ N, (CH ₃ ) ₂ HSiNHSi(CH ₃ ) ₂ H, CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ CH ₂ CH ₂ CF ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ CH ₂ CH ₂ C ₂ F ₅ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ CH ₂ CH ₂ C ₃ F ₇ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ CH ₂ CH ₂ C ₄ F ₉ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ ) ₂ NHSi (CH ₃ ) ₂ CH ₂ CH ₂ C ₅ F ₁₁ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ CH ₂ CH ₂ C ₆ F ₁₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ CH ₂ CH ₂ C ₇ F ₁₅ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ NHSi(CH ₃ ) ₂ CH ₂ CH ₂ C ₈ F ₁₇ , a compound such as {CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ } ₃ N.

Examples of the above alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, isobutanol, 1-pentanol, and 1-hexanol. , 1-heptanol, 1-octanol, etc., an alcohol having an alkyl group and a hydroxyl group, ethylene glycol, glycerin, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,2-pentanediol, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Such as a polyol or a derivative thereof.

Further, when an alcohol having one hydroxyl group at the terminal of the linear alkyl group is used, the protective film can be formed in a short period of time, which is preferable, and further, if the linear chain is used When the number of carbon atoms of the alkyl group is from 1 to 6, the protective film can be formed in a short period of time, which is particularly preferable.

In the case where the reaction is carried out as described above, the total amount of water in the chemical solution forming solution is preferably 5,000 ppm by mass or less based on the total amount of the chemical solution. In this case, the amount of water in the raw material is preferably as small as possible, and particularly preferably 1000 ppm by mass or less, and further preferably 500 ppm by mass or less. Further, the total amount of water in the raw material may be 0.1 mass ppm or more. Therefore, the hydrazine compound B or the hydrazine compound D and the alcohol used in the above reaction preferably do not contain a large amount of water, and the water content is preferably 5,000 ppm by mass or less. When the amount is more than 5,000 ppm by mass, the reaction of the above formulas [3], [6], and [7] is difficult to proceed, and it is difficult to obtain a desired chemical solution for forming a protective film. Therefore, the amount of the hydrazine compound B or the hydrazine compound D and the alcohol used in the above reaction is preferably as small as possible, and particularly preferably 1000 ppm by mass or less, and further preferably 500 ppm by mass or less. In addition, when the amount of water is large, the storage stability of the chemical liquid is liable to lower. Therefore, the amount of water is preferably as small as possible, and is preferably 200 ppm by mass or less, and more preferably 100 ppm by mass or less. Further, the total amount of water in the raw material may be 0.1 mass ppm or more.

Further, in the case where the reaction is carried out as described above, when the particles are measured by the light scattering type liquid particle detector in the liquid phase in the protective film forming liquid, the number of particles larger than 0.5 μm is per 1 mL of the drug. The liquid is also preferably 100 or less. If the number of particles larger than 0.5 μm is more than 100 per 1 mL of the chemical solution, the pattern damage caused by the particles is caused, and the component yield is lowered and the reliability is lowered. Not good. Moreover, when the number of particles larger than 0.5 μm is 100 or less per 1 mL of the chemical liquid, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Therefore, the number of particles larger than 0.5 μm in the above-mentioned chemical liquid is preferably as small as possible per 1 mL of the chemical liquid, and particularly preferably 10 or less, more preferably 2 or less. Further, the number of particles larger than 0.5 μm may be one or more per 1 mL of the chemical solution.

Further, in the case where the reaction is obtained as described above, the content of the metal impurities of each of Na, Mg, K, Ca, Mn, Fe, and Cu in the protective film forming liquid is also relatively larger than the total amount of the liquid. The best is 100 mass ppb or less. When the content of the metal impurities exceeds 100 mass ppb with respect to the total amount of the chemical liquid, the junction leakage current of the element increases, which causes a decrease in the component yield and a decrease in reliability, which is not preferable. In addition, when the content of the metal impurities is 100 mass ppb or less with respect to the total amount of the chemical liquid, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Therefore, the metal impurity content is preferably as small as possible, and particularly preferably 1 mass ppb or less, and more preferably 0.1 mass ppb or less. Further, the content of the metal impurities may be 0.01 mass ppb or more with respect to the total amount of the chemical liquid, respectively.

In the case where the hydrazine compound B and the alcohol are used as the raw material of the protective liquid for forming a protective film, it is preferred to purify at least one of the hydrazine compound B, the alcohol, and the mixed liquid mixture before mixing. Further, when the chemical solution forming solution contains a solvent, the hydrazine compound B and the alcohol before the mixing may be in a solution state containing a solvent. In this case, the above-mentioned purification may also be carried out before the hydrazine compound B or a solution thereof. Alcohol or its solution, and mixed mixture At least one of the combined liquids is targeted.

In the case where the hydrazine compound D and the alcohol are used as the raw material of the protective liquid for forming a protective film, it is preferred to purify at least one of the hydrazine compound D, the alcohol, and the mixed liquid mixture before mixing. In the case where the chemical solution forming solution contains a solvent, the above purification may be carried out by at least one of the above-mentioned hydrazine compound D or a solution thereof, an alcohol or a solution thereof, and a mixed liquid mixture.

The above purification uses removal of metal impurities such as an element such as Na, Mg, K, Ca, Mn, Fe, and Cu by an ion exchange resin or distillation, such as removal of water molecules by an adsorbent such as a molecular sieve or distillation, or the like. And at least one of removing the pollutants such as particles filtered by the filter. It is preferable to consider the activity or cleanliness of the protective film forming liquid, remove water molecules, remove metal impurities, and remove contaminants regardless of the order of removal.

Further, it is preferred that the above alcohol and the solvent remove moisture before being mixed with the above-mentioned hydrazine compound B or hydrazine compound D. Therefore, when the chemical solution for forming a protective film is prepared, it is preferred to reduce the amount of moisture without deactivating the produced hydrazine compound A or hydrazine compound C or an acid or a base. Therefore, the smaller the respective moisture content, the better, each preferably 10,000 ppm by mass or less, and each of them is desirably infinitely close to 0 ppm by mass.

Further, the chemical solution for forming a protective film of the present invention may contain other additives or the like in addition to the above-mentioned hydrazine compound A, hydrazine compound C, acid or base, or a solvent, within a range not inhibiting the object of the present invention. Examples of the additive include oxidizing agents such as hydrogen peroxide and ozone, and surfactants. also, When a material which does not form a protective film from the above-mentioned cerium compound A or cerium compound C exists in one of the concave-convex patterns of the wafer, a protective film may be added to the material. Further, other acids or bases may be added for purposes other than the catalyst.

In addition, the chemical solution for forming a protective film of the present invention may be stored in a state in which the raw materials are classified into two or more kinds and used in combination before use. For example, when the hydrazine compound A or the acid is used as a part of the raw material of the protective film forming chemical solution, the hydrazine compound A and the acid may be separately stored and mixed before use. Further, the hydrazine compound A and the acid before mixing may also be in a solution state. Further, the hydrazine compound A and the acid may be stored in the same solution and mixed with a solution containing other raw materials before use. When the hydrazine compound B and the alcohol are used, the hydrazine compound B and the alcohol may be separately stored and mixed before use. Further, the hydrazine compound B and the alcohol before mixing may also be in a solution state. Further, the above-mentioned hydrazine compound B and an alcohol may be stored in the same solution and mixed with other raw materials before use.

Similarly, when the hydrazine compound C or the base is used, the hydrazine compound C and the base may be separately stored and mixed before use. Further, the hydrazine compound C and the base before mixing may also be in a solution state. Further, the hydrazine compound C and the base may be stored in the same solution and mixed with a solution containing other raw materials before use. When the hydrazine compound D and the alcohol are used, the hydrazine compound D and the alcohol may be separately stored and mixed before use. Further, the hydrazine compound D and the alcohol before mixing may also be in a solution state. Further, the above-mentioned hydrazine compound D and an alcohol may be stored in the same solution and mixed with other raw materials before use.

Further, as the chemical solution for forming a protective film of the present invention, for example, a mixture containing or a mixture containing hydrofluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, alcohol, and polyol may be used. At least one or more organic solvents in the group consisting of or a derivative thereof are 76 to 99.99% by mass, and are selected from a group having a _Cy H _2y+1 group or a _Cy F _2y+1 CH ₂ CH ₂ group (y=1~). 8) at least one or more ruthenium compounds of the group consisting of alkoxy decane or chlorodecane, trimethyl decyl perfluoroalkyl sulfonate, and trimethyl decyl trifluoroacetate 0.1 to 20 The mass% and the acid selected from the group consisting of trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride are 0 to 4% by mass. Further, when the ruthenium compound is only alkoxy decane or when the organic solvent does not contain an alcohol, the concentration of the above acid is set to 0.01 to 4% by mass. Further, for example, a mixture comprising or a mixture containing only a group selected from the group consisting of hydrofluorocarbons, hydrofluoroethers, hydrochlorofluorocarbons, alcohols, and polyhydric alcohols or derivatives thereof may be used. At least one or more organic solvents are 76 to 99.99% by mass, and are selected from _alkoxydecane having a _Cy H _2y+1 group or a _Cy F _2y+1 CH ₂ CH ₂ group (y=2 to 8). At least one or more kinds of ruthenium compounds of the group consisting of alkoxy decane and tetramethyldiazepine are 0.1 to 20% by mass, and at least one selected from the group consisting of ammonia and alkylamine The base is 0 to 4% by mass. Further, when the ruthenium compound is only alkoxy decane or when the organic solvent does not contain an alcohol, the concentration of the above base is set to 0.01 to 4% by mass.

In the pattern forming step of forming the surface of the wafer as a surface having a fine uneven pattern, first, after applying a resist on the surface of the wafer, the resist is exposed through a resist mask, and the etching is removed by etching. Exposure resist, or An unexposed resist is used to thereby form a resist having a desired concavo-convex pattern. Further, even if a mold having a pattern is pressed against the resist, a resist having a concavo-convex pattern can be obtained. The wafer is then etched. At this time, the concave portion of the resist pattern is selectively etched. Finally, when the resist is peeled off, a wafer having a fine concavo-convex pattern is obtained.

A wafer having a fine concavo-convex pattern on its surface and at least a part of the concavo-convex pattern containing a hafnium element includes a film having a tantalum element such as tantalum, niobium oxide or tantalum nitride formed on the surface of the wafer, or forming the above-mentioned unevenness In the case of a pattern, at least a part of the surface of the uneven pattern contains a ruthenium element such as ruthenium, iridium oxide or tantalum nitride.

Further, a protective film may be formed on at least one surface selected from the group consisting of ruthenium, iridium oxide and tantalum nitride with respect to a wafer composed of a plurality of components selected from at least one selected from the group consisting of ruthenium, iridium oxide and tantalum nitride. . The wafer composed of the plurality of components further includes at least one selected from the group consisting of tantalum, niobium oxide, and tantalum nitride formed on the surface of the wafer, or at least a portion of the concave and convex pattern is also selected when the concave and convex pattern is formed. At least one of ruthenium, ruthenium oxide and ruthenium nitride. Further, the protective film formed of the chemical solution of the present invention may be formed on the surface of the portion containing the ruthenium element in the concave-convex pattern.

When the surface of the wafer is a surface having a fine uneven pattern, if the surface is washed with a water-based cleaning solution and the aqueous cleaning solution is removed by drying or the like, the width of the concave portion is narrow, and if the vertical and horizontal portions of the convex portion are relatively large, It is prone to pattern collapse. This concave-convex pattern is defined as shown in FIGS. 1 and 2 . Fig. 1 is a schematic plan view showing a wafer 1 having a surface having a surface having a fine uneven pattern 2, and Fig. 2 is a view showing a portion of the a-a' cross section of Fig. 1. The width of the recess 5 is like 2 is shown by the interval between the convex portion 3 and the convex portion 3, and the aspect ratio of the convex portion is represented by the height 6 of the convex portion divided by the width 7 of the convex portion. The pattern collapse in the cleaning step is likely to occur when the width of the concave portion is 70 nm or less, particularly 45 nm or less, and the aspect ratio is 4 or more, particularly 6 or more.

In a preferred aspect of the present invention, as shown in the above (Step 1), after the surface of the wafer is a surface having a fine uneven pattern, the aqueous cleaning solution is supplied to the surface to at least the concave surface of the concave-convex pattern. Keep the water-based cleaning solution. Then, as shown in the above (Step 2), the aqueous cleaning liquid held on the surface of at least the concave portion of the concave-convex pattern is replaced with the cleaning liquid A different from the aqueous cleaning liquid. Preferred examples of the cleaning solution A include a chemical solution for forming a protective film specified in the present invention, water, an organic solvent, or a mixture thereof, or an acid, a base or a surfactant mixed therein. At least one of the oxidants and the like. In addition, when the cleaning liquid A is used in addition to the above-mentioned chemical liquid, it is preferable to gradually replace the cleaning liquid A with the cleaning liquid A while maintaining the cleaning liquid A on the surface of at least the concave portion of the concave-convex pattern. Use liquid medicine.

Moreover, examples of the organic solvent which is one of preferable examples of the cleaning liquid A include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, anthraquinone solvents, alcohols, and polyols. Derivatives, nitrogen-containing compound solvents, and the like.

Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane; and examples of the ester include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetate. Etc.; as an example of the above ethers, there are diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, two An alkane or the like; as an example of the ketone, acetone, ethyl acetonide, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone or the like; as the above halogen-containing solvent For example, perfluorooctane, perfluorodecane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, etc., perfluorocarbon, 1,1,1,3,3-pentafluorobutane, octafluoro Hydrofluorocarbon such as cyclopentane, 2,3-dihydro decafluoropentane, Zeorora H (manufactured by ZEON, Japan), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, B Hydrofluoroethers such as perfluoroisobutyl ether, Asahiklin AE-3000 (made by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 (all manufactured by 3M), chlorocarbon such as tetrachloromethane, chloroform Hydrochlorofluorocarbon, chlorofluorocarbon such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2 , 3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, etc. Hydrochlorofluorocarbon, perfluoroether, perfluoropoly Examples of the above-mentioned anthraquinone-based solvent include dimethyl hydrazine and the like; and examples of the alcohol include methanol, ethanol, propanol, butanol, ethylene glycol, and 1,3-propanediol. As examples of the above derivatives of the polyol, there are diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate Ester, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ether, diethylene glycol diethyl ether, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, etc. As examples of the solvent of the nitrogen-containing compound, there are methotrexate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, diethylamine, and the like. Ethylamine, pyridine, and the like.

Further, as an acid which may be mixed in the cleaning liquid A, there may be an inorganic acid or an organic acid. Examples of the inorganic acid include hydrofluoric acid and buffered hydrofluoric acid. Examples of the organic acid include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, etc., and examples thereof include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid, and pentafluoropropionic acid. Examples of the base which may be mixed in the cleaning solution A include ammonia, choline, and the like. Examples of the oxidizing agent that may be mixed in the cleaning liquid A include ozone, hydrogen peroxide, and the like.

In addition, when the cleaning liquid A is an organic solvent, the protective film forming chemical solution can be supplied to the concave portion without coming into contact with water, which is preferable. In particular, when the organic solvent contains a water-soluble organic solvent (the solubility of 100 parts by mass or more of water is 5 parts by mass or more), it is easy to replace the aqueous cleaning solution with the cleaning liquid A, which is preferable. Moreover, when the cleaning liquid A contains an aqueous acid solution, the protective film can be formed in a short time, which is preferable.

Further, as the cleaning liquid A, a plurality of cleaning liquids may be used. For example, a cleaning solution containing an aqueous acid solution or an aqueous alkali solution and the above organic solvent (preferably containing a water-soluble organic solvent) may be used for the cleaning liquid A, and the cleaning liquid containing an aqueous acid solution or an aqueous alkali solution may be used. → The order of the above organic solvents is washed. Further, the aqueous cleaning solution may be added, and the aqueous cleaning solution may be washed in the order of the aqueous solution containing the acid aqueous solution or the aqueous alkali solution, the aqueous cleaning solution, and the organic solvent.

FIG. 3 is a schematic view showing a state in which the protective film forming chemical liquid 8 is held by the concave portion 4 by the washing step. The wafer of the schematic diagram of Figure 3 represents a portion of the a-a' section of Figure 1. At the time of the washing step, the protective film forming chemical solution is supplied to the wafer 1 on which the uneven pattern 2 is formed. At this time, the chemical liquid is held in the concave portion 4 as shown in FIG. 3, and a protective film is formed on the surface of the concave portion 4, whereby the surface is water-repellent.

When the temperature is raised, the protective film forming chemical liquid is liable to form the protective film in a shorter period of time. The temperature at which the homogeneous protective film is easily formed is preferably 10 ° C or more and does not reach the boiling point of the chemical liquid, and is particularly preferably maintained at 15 ° C or higher and less than 10 ° C lower than the boiling point of the chemical liquid. It is preferable that the temperature of the chemical liquid is maintained at the temperature when it is held on at least the surface of the concave portion of the concave-convex pattern.

Further, the other washing liquid may be maintained at a temperature of 10 ° C or more and not reaching the boiling point of the washing liquid. For example, when the cleaning liquid A is a solution containing an aqueous acid solution, particularly preferably an aqueous acid solution and an organic solvent having a boiling point of 100 ° C or higher, if the temperature of the cleaning liquid is raised to the vicinity of the boiling point of the cleaning liquid, It is easy to form the above protective film in a short time, and therefore it is preferable.

The step of maintaining the protective film forming solution on at least the surface of the concave portion of the concave-convex pattern (step 3), and replacing the chemical liquid held on the surface of at least the concave portion of the concave-convex pattern with the chemical liquid After the cleaning liquid B, the step of removing the liquid from the surface of the concave-convex pattern by drying is carried out (step 4). Examples of the cleaning liquid B include an aqueous cleaning solution containing an aqueous solution, or an organic solvent. Or a mixture of the aqueous cleaning solution and the organic solvent, wherein at least one of an acid, an alkali, and a surfactant is mixed, or a chemical liquid is contained in the protective film forming liquid. The compound A and the acid or the above-mentioned hydrazine compound C and a base are obtained until the concentration is lower than the drug solution.

Moreover, examples of the organic solvent which is one of preferable examples of the cleaning liquid B include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, anthraquinone solvents, alcohols, and polyols. Derivatives, nitrogen-containing compound solvents, and the like.

Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane; and examples of the ester include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetate. Etc.; as an example of the above ethers, there are diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, two An alkane or the like; as an example of the ketone, acetone, ethyl acetonide, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone or the like; as the above halogen-containing solvent For example, perfluorooctane, perfluorodecane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, etc., perfluorocarbon, 1,1,1,3,3-pentafluorobutane, octafluoro Hydrofluorocarbon such as cyclopentane, 2,3-dihydro decafluoropentane, Zeorora H (manufactured by ZEON, Japan), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, B Hydrofluoroethers such as perfluoroisobutyl ether, Asahiklin AE-3000 (made by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 (all manufactured by 3M), chlorocarbon such as tetrachloromethane, chloroform Hydrochlorofluorocarbon, chlorofluorocarbon such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2 , 3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, etc. Hydrochlorofluorocarbon, perfluoroether, perfluoropoly Examples of the above-mentioned anthraquinone-based solvent include dimethyl hydrazine and the like; and examples of the alcohol include methanol, ethanol, propanol, butanol, ethylene glycol, and 1,3-propanediol. As examples of the above derivatives of the polyol, there are diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate Ester, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ether, diethylene glycol diethyl ether, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, etc. As examples of the solvent of the nitrogen-containing compound, there are methotrexate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, diethylamine, and the like. Ethylamine, pyridine, and the like.

Further, after the water-based cleaning liquid containing the aqueous solution is retained on the surface of at least the concave portion of the concave-convex pattern by the replacement of the cleaning liquid B, the step of transitioning to the surface of the concave-convex pattern by drying may be carried out (step 4). ).

Further, as the cleaning liquid B, a plurality of cleaning liquids may be used. For example, an organic solvent (preferably comprising a water-soluble organic solvent) and an aqueous cleaning solution can be used.

Examples of the water-based cleaning liquid include water in which at least one of an organic solvent, an acid, and a base is mixed with water as a main component (for example, a water content of 50% by mass or more). . In particular, when water is used in the aqueous cleaning solution, at least the contact angle θ between the surface of the concave portion of the concave-convex pattern which is repellent by the chemical liquid and the liquid is increased, so that the capillary force P of the surface of the concave portion is lowered, and then dried. It is preferable that the dirt is hard to remain on the surface of the wafer.

A schematic diagram of a state in which a water-based cleaning liquid is held in the recessed portion 4 which is water-repellent by the protective film forming chemical solution is shown in Fig. 4 . The wafer of the pattern of Figure 4 represents a portion of the a-a' section of Figure 1. The surface of the concave-convex pattern is water-repellent by forming the protective film 10 from the above chemical liquid. Further, when the protective film 10 is removed from the surface of the concave-convex pattern, it is also held on the surface of the wafer.

When the protective film 10 is formed on the surface of at least the concave portion of the concave-convex pattern of the wafer by the protective film forming chemical solution, if the contact angle is 60 to 120° when water is held on the surface, it is difficult to cause pattern collapse. Preferably. Further, the closer the contact angle is to 90°, the smaller the capillary force of the surface of the concave portion is, and the pattern collapse is hard to occur, so that it is more preferably 70 to 110°, still more preferably 75 to 105°. Further, the capillary force is preferably 1.6 MN/m ² or less. When the capillary force is 1.6 MN/m ² or less, pattern collapse is less likely to occur, which is preferable. Further, when the capillary force is reduced, the pattern collapse is less likely to occur. Therefore, the capillary force is preferably 1.1 MN/m ² or less, and more preferably 0.8 MN/m ² or less. Further, it is preferable to adjust the contact angle with the cleaning liquid to a vicinity of 90° so that the capillary force is infinitely close to 0.0 MN/m ² .

Then, as shown in the above (Step 4), a step of removing the liquid from the surface of the concave-convex pattern by drying is performed. In this step, the liquid held on the surface of the concave-convex pattern is removed by drying. The drying is preferably carried out by a known drying method such as spin drying, IPA (2-propanol) vapor drying, malangani drying, heat drying, warm air drying, and vacuum drying.

When the liquid is removed from the surface of the concave-convex pattern, the liquid held on the surface may be the chemical liquid, the cleaning liquid B, the aqueous cleaning liquid, and the mixed liquid. Further, the mixed solution containing the chemical liquid may be a liquid in a state in which the chemical liquid is replaced with the cleaning liquid B, or the chemical liquid may be mixed in advance in a washing liquid different from the chemical liquid. The mixture obtained. Further, after temporarily removing the liquid from the surface of the concave-convex pattern, at least one selected from the cleaning liquid B, the aqueous cleaning liquid, and the mixed liquid may be held on the surface of the concave-convex pattern, and then dried.

Then, as shown in the above (step 5), the step of removing the protective film 10 is performed. In the case of removing the above protective film, it is effective to cut off the C-C bond and the C-F bond in the protective film. The method is not particularly limited as long as the bonding can be cut, and examples thereof include a process of irradiating a surface of a wafer with light, a process of heating a wafer, and a process of exposing the wafer to ozone. The surface of the wafer is subjected to plasma irradiation treatment, and the surface of the wafer is subjected to corona discharge treatment.

When the protective film 10 is removed by light irradiation, it is effective to cut the CC bond and the CF bond in the protective film 10. For this purpose, it is preferred to irradiate ultraviolet rays having a relatively high equivalent The energy of 83 kcal/mol and 116 kcal/mol of the bonding energy is a shorter wavelength of 340 nm and 240 nm. As the light source, a metal halide lamp, a low pressure mercury lamp, a high pressure mercury lamp, an excimer lamp, a carbon arc lamp or the like is used. In the case of a metal halide lamp, the ultraviolet irradiation intensity is measured by, for example, an illuminance meter (illumination unit UM-10 manufactured by Konica Minolta Sensing, light receiving unit UM-360 [peak sensitivity wavelength: 365 nm, measurement wavelength range: 310 to 400 nm]). The value is preferably 100 mW/cm ² or more, and particularly preferably 200 mW/cm ² or more. Further, if the irradiation intensity is less than 100 mW/cm ² , it takes a long time to remove the protective film 10 described above. Further, in the case of a low-pressure mercury lamp, ultraviolet rays having a shorter wavelength are irradiated. Therefore, even if the irradiation intensity is low, the protective film 10 can be removed in a short time, which is preferable.

In the case where the protective film 10 is removed by light irradiation, when the constituent components of the protective film 10 are decomposed by ultraviolet rays and ozone is generated at the same time, the constituents of the protective film 10 are oxidized and volatilized by the ozone. The processing time is shortened, so it is especially preferred. As the light source, a low pressure mercury lamp or an excimer lamp is used. Further, the wafer may be heated while being irradiated with light.

In the case of heating the wafer, the wafer is heated at 400 to 700 ° C, preferably 500 to 700 ° C. The heating time is preferably maintained at 0.5 to 60 minutes. The clock is preferably 1 to 30 minutes. Further, in this step, ozone exposure, plasma irradiation, corona discharge, or the like may be used in combination. Further, it is also possible to perform light irradiation while heating the wafer.

In the case where the wafer is subjected to ozone exposure, it is preferable to supply ozone generated by ultraviolet irradiation such as a low-pressure mercury lamp or the like by low-temperature discharge of a high voltage or the like to the wafer surface. It is also possible to perform ozone exposure on the wafer, and to perform light irradiation or heating.

In the step of removing the protective film on the surface of the wafer, the protective film on the surface of the wafer can be effectively removed by combining light irradiation treatment, heat treatment, ozone exposure treatment, plasma irradiation treatment, corona discharge treatment, or the like.

The chemical solution of the present invention may be one liquid type which is contained by mixing the above-mentioned hydrazine compound A with the above-mentioned acid, or may be used as a liquid type containing the above hydrazine compound A and a liquid type containing the above-mentioned acid. Mixer. Further, it may be a two-liquid type of a liquid containing the above-mentioned hydrazine compound B and a liquid containing the above-mentioned alcohol. Further, the chemical solution of the present invention may be one liquid type which is contained by mixing the above-mentioned hydrazine compound C with the above-mentioned base, or may be a two-liquid type which is a liquid containing the above-mentioned hydrazine compound C and a liquid containing the above-mentioned alkali. Mixer when in use. Further, it may be a two-liquid type of a liquid containing the above-mentioned hydrazine compound D and a liquid containing the above-mentioned alcohol.

Example

The case where the surface of the wafer is a surface having a fine uneven pattern and the case where the cleaning liquid held on at least the surface of the concave portion of the concave-convex pattern is replaced with another cleaning liquid has been established in various other literatures and the like. Technology, therefore, in the present invention, the evaluation of the above-mentioned protective film forming liquid Discuss for the center. Further, as defined by the formula P = 2 × γ × cos θ / S (γ: surface tension, θ: contact angle, S: pattern size) described in the prior art, etc., the pattern collapse largely depends on the cleaning liquid and the crystal. The contact angle of the round surface, that is, the contact angle of the droplets and the surface tension of the cleaning liquid. When the cleaning liquid is held in the concave portion 4 of the concave-convex pattern 2, the contact angle of the liquid droplets is correlated with the capillary force of the surface of the concave portion which is considered to be equivalent to the pattern collapse, and therefore, according to the above formula and the protective film 10 The evaluation of the contact angle of the droplets leads to capillary forces. Further, in the examples, water as a representative of the aqueous washing liquid was used as the washing liquid.

However, in the case of a wafer having a fine uneven pattern on the surface, since the pattern is very fine, the contact angle of the protective film 10 itself formed on the surface of the uneven pattern cannot be accurately evaluated.

The evaluation of the contact angle of the water droplets is also disclosed in JIS R 3257 "Test method for wettability of the surface of the substrate glass" by dropping a few μl of water droplets on the surface of the sample (substrate), and measuring the surface of the water droplets and the substrate. It is carried out at the angle of formation. However, in the case of a patterned wafer, the contact angle becomes very large. The reason for this is that a Wenzel effect or a Cassie effect is produced, so that the contact angle affects the surface shape (roughness) of the substrate and increases the contact angle of the water droplets on the appearance.

Therefore, in the present invention, the chemical liquid is supplied to a wafer having a smooth surface to form a protective film on the surface of the wafer, and the protective film is formed on the surface of the wafer 1 on which the fine uneven pattern 2 is formed. The film 10 was protected and subjected to various evaluations. Furthermore, in the present invention, as a surface smooth wafer, a surface having a thermal oxide film layer or a tantalum nitride layer or a polysilicon layer is used and the surface is flat. Sliding on the wafer.

The details are described below. In the following, the evaluation method of the wafer to which the protective film forming chemical liquid is supplied, the preparation of the protective film forming chemical liquid, and the evaluation result after the protective film forming chemical liquid is supplied to the wafer will be described.

[Evaluation method of wafer supplied with protective film forming liquid]

As evaluation methods of the wafer to which the protective film formation liquid is supplied, the following evaluations (1) to (4) were performed.

(1) Evaluation of contact angle of protective film formed on the surface of the wafer

About 2 μl of pure water was placed on the surface of the wafer on which the protective film was formed, and the angle (contact angle) formed by the water droplets on the surface of the wafer was measured by a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.: CA-X type).

(2) Evaluation of capillary force

P was calculated using the following formula, and the capillary force (absolute value of P) was obtained.

P = 2 × γ × cos θ / S Here, γ represents the surface tension, θ represents the contact angle, and S represents the pattern size. Further, in the present embodiment, as an example of the pattern shape, a wafer having a line width (width of the concave portion) of a line of 45 nm and a pattern of a line and space shape is assumed. The line width: the pattern of 45 nm has a tendency that when the cleaning liquid at the gas-liquid interface passes through the wafer is water, the pattern is liable to collapse, and when the cleaning liquid is 2-propanol, the pattern is hard to collapse. In the case of pattern size: 45 nm, wafer surface: yttrium oxide, when the cleaning solution is 2-propanol (surface tension: 22 mN/m, contact angle with yttrium oxide: 1°), the capillary force becomes 0.98 MN. /m ² . On the other hand, when the washing liquid is water having the largest surface tension in the liquid other than mercury (surface tension: 72 mN/m, contact angle with cerium oxide: 2.5°), the capillary force becomes 3.2 MN/m ² . The capillary force is preferably 1.6 MN/m ² or less, more preferably 1.1 MN/m ² or less, and particularly preferably 0.8 MN/m ² or less.

(3) Removal of protective film

The sample was irradiated with UV light of a metal halide lamp for 2 hours under the following conditions. When the contact angle of the water droplets after irradiation was 30 or less, it was set as the pass (the table is indicated by ○).

‧Light: M015-L312 manufactured by EYE GRAPHICS

(strength: 1.5kW)

‧ Illuminance: The measured value under the following conditions is 128 mW/cm ²

‧Measurement device: UV intensity meter

(Manufactured by Konica Minolta Sensing, UM-10)

‧Receiver Department: UM-360

(receiving wavelength: 310~400nm, peak wavelength: 365nm)

‧ Measurement mode: illuminance measurement

(4) Surface smoothness evaluation of the wafer after removing the protective film

The surface was observed by an atomic force electron microscope (manufactured by Seiko Instruments: SPI3700, 2.5 μm square scan) to obtain an average surface roughness of the center line: Ra (nm). In addition, the Ra system applies the center line average roughness defined in JIS B 0601 to the measurement surface and expands to a three-dimensional shape as the value obtained by averaging the absolute values of the difference between the reference surface and the designated surface. Calculated by the formula. When the Ra value of the wafer after removing the protective film is 1 nm or less, the surface of the wafer is not eroded by the cleaning, and the residue of the protective film does not exist on the surface of the wafer, so it is qualified (the table is marked as ○) ).

Here, X _L , X _R , Y _B , and Y _T represent the measurement ranges of the X coordinate and the Y coordinate, respectively. S ₀ is an area when the measurement surface is ideally flat, and is set to a value of (X _R - X _L ) × (Y _{B -} Y _T ). Further, F(X, Y) represents the height of the measurement point (X, Y), and Z ₀ represents the average height in the measurement plane.

[Example 1]

(1) Modulation of protective film forming liquid

As a semiconductor-grade trimethyl methoxy decane [(CH ₃ ) ₃ SiOCH ₃ ]: 3 g, as a semiconductor semiconductor grade trifluoromethanesulfonic acid [CF ₃ SO ₃ H]: 1 g, A semiconductor-grade fluorine-based solvent of organic solvent (Novec HFE-7100: hydrofluoroether manufactured by Sumitomo 3M): 96 g is mixed to obtain a protective film-forming chemical solution. Further, water is removed from the chemical solution by molecular sieve 4A (manufactured by Shogo Co., Ltd.), and then metal impurities are removed from the chemical solution by ion exchange resin (ION-CLEAN SL manufactured by Nihon Pall), followed by filtration. The particles were removed from the solution by filtration (Optimizer manufactured by Entegris, Japan) and purified. The amount of water in the purified liquid is measured by a Karl Fischer type moisture meter (manufactured by Kyoto Electronics, ADP-511 type), and as a result, the amount of water in the liquid after purification is relative to the liquid The total amount is 8 mass ppm. Further, the content of the metal impurities in the purified liquid solution was measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical System, Agilent 7500cs type), and the purified Na, Mg, K, The content of metal impurities of each element of Ca, Mn, Fe and Cu is Na=3 mass ppb, Mg=0.03 mass ppb, K=0.4 mass ppb, Ca=6 mass ppb, Mn= relative to the total amount of the liquid solution. 0.003 mass ppb, Fe=0.2 mass ppb, Cu=0.04 mass ppb. In the liquid phase measurement by the particle detector in the liquid-scattering liquid particle detector, the number of particles larger than 0.5 μm is measured by a light scattering liquid particle measuring device (Model KS-42AF, manufactured by Rion Co., Ltd.), and the result is larger than The number of particles of 0.5 μm was 3 per 1 mL of the drug solution. Further, in the examples after the present example, the same purification was used, and it was confirmed that the water content was 5000 mass ppm or less with respect to the total amount of the chemical liquid, and each of Na, Mg, K, Ca, Mn, Fe, and Cu was used. The metal impurity content of the element is 100 mass ppb or less and the number of particles larger than 0.5 μm is 100 or less per 1 mL of the chemical liquid, respectively.

(2) Washing the wafer

The smoothed silicon wafer with a thermal oxide film (Si wafer having a thermal oxide film layer having a thickness of 1 μm on the surface) was immersed in a 1% by mass aqueous solution of hydrofluoric acid at room temperature for 2 minutes, followed by 80 The mixture was immersed in a 3 mass% aqueous hydrogen peroxide solution at ° C for 2 minutes, further immersed in pure water at room temperature for 1 minute, and immersed in 2-propanol (iPA) at room temperature for 1 minute.

(3) Surface treatment of the surface of the wafer using the protective film forming solution

The tantalum wafer was immersed in the protective film forming chemical solution prepared in the above-mentioned "(1) Preparation of Protective Solution Forming Chemical Solution" at 20 ° C for 5 minutes. Thereafter, the ruthenium wafer was immersed in iPA for 1 minute, and then immersed in pure water as a water-based cleaning solution for 1 minute. Finally, the silicon wafer is taken out of the pure water, and air is sprayed to remove the pure water on the surface.

The wafer obtained by the evaluation of the point disclosed in the above-mentioned "Method for evaluating a wafer for supplying a protective film forming liquid" is as shown in Table 1, and the initial contact angle before surface treatment is less than 10°. The subsequent contact angle was 86°, showing a water repellency imparting effect. Further, the capillary force when water was held was calculated using the formula disclosed in "Evaluation of Capillary Force", and as a result, the capillary force was 0.2 MN/m ² and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

[Examples 2 to 57]

The conditions of the ruthenium compound A (矽 compound C), the concentration of the ruthenium compound A, the concentration of the acid and the acid, the alkali, the organic solvent, and the treatment sequence after the surface treatment of the protective film forming solution are changed, and the conditions are changed. The surface treatment of the wafer was carried out, and the evaluation was performed. The results are shown in Tables 1 to 2.

Further, in the table, "(CH ₃ ) ₃ SiCl" means trimethylchloromethane, and "(CH ₃ ) ₂ Si(H)OCH ₂ CH ₃ " means dimethyl ethoxy decane, "( CH ₃ ) ₃ SiOSi(CH ₃ ) ₃ ” means hexamethyldioxane.

Further, in the table, "CTFP" means 1-chloro-3,3,3-trifluoropropene, and "DCTFP" means cis-1,2-dichloro-3,3,3-trifluoropropene, " "PGMEA" means propylene glycol monomethyl ether acetate, and "HFE-7100/PGMEA" means a mixed solvent of HFE-7100:PGMEA=95:5 by mass ratio. "CTFP/PGMEA" means a mixed solvent of CTFP:PGMEA=95:5 by mass ratio. "DCTFP/PGMEA" means a mixed solvent of DCTFP: PGMEA = 95:5 by mass ratio. "HFE-7100/iPA" means a mixed solvent of HFE-7100 and iPA, and the concentration (alcohol concentration) of the alcohol in the protective film forming solution is 5% by mass. "CTFP/iPA" means a mixed solvent of CTFP and iPA, and the concentration (alcohol concentration) of the alcohol in the protective film forming solution is 5% by mass. "DCTFP/iPA" means a mixed solvent of DCTFP and iPA, and the concentration (alcohol concentration) of the alcohol in the protective film forming solution is 5% by mass.

Further, in the table, "CH ₃ SO ₃ H" means methanesulfonic acid as an acid, "H ₂ SO ₄ " means 98% sulfuric acid as an acid, and "(CH ₃ ) ₃ SiOSO ₂ CF ₃ " means As the acid trimethyldecyltrifluoromethanesulfonate, "(CF ₃ SO ₂ ) ₂ O" means trifluoromethanesulfonic anhydride as an acid, and "DEA" means diethylamine as a base.

In the above-mentioned "(3) surface treatment by the chemical solution for forming a protective film on the surface of the wafer," the ruthenium wafer is immersed in the chemical solution for forming a protective film, and then immersed in pure. 1 minute in water, and finally from pure water The silicon wafer is taken out and air is sprayed to remove pure water from the surface.

In the above-mentioned "(3) Surface treatment by the chemical solution for forming a protective film on the surface of the wafer," the ruthenium wafer was immersed in the chemical solution for forming a protective film, and then immersed in the iPA. In the middle of 1 minute, the wafer was finally taken out from the iPA, and air was sprayed to remove the surface iPA.

In the above-mentioned "(3) Surface treatment by the chemical solution for forming a protective film on the surface of the wafer," in the above-mentioned "39", the air is discharged from the protective film forming liquid, and then the air is sprayed. The protective film forming solution for removing the surface is removed.

In the above-mentioned "(3) Surface treatment by the chemical solution for forming a protective film on the surface of the wafer," in the above-mentioned "43", the ruthenium wafer was immersed in the chemical solution for forming a protective film, and then air was sprayed. The protective film forming liquid for removing the surface is removed. Then, it was immersed in pure water for 1 minute, and finally the silicon wafer was taken out from the pure water, and air was sprayed to remove the pure water on the surface.

In the above-mentioned "(3) Surface treatment by the chemical solution for forming a protective film on the surface of the wafer," in the above-mentioned "45", the ruthenium wafer was immersed in the chemical solution for forming a protective film, and then air was sprayed. The protective film forming liquid for removing the surface is removed. Then, it was immersed in iPA for 1 minute, and finally the ruthenium wafer was taken out from the iPA, and air was sprayed to remove the surface iPA.

In the above-mentioned "(3) Surface treatment by the chemical solution for forming a protective film on the surface of the wafer," in the above-mentioned "47", the ruthenium wafer was immersed in the chemical solution for forming a protective film, and then air was sprayed. The protective film forming liquid for removing the surface is removed. Then, immersed in iPA for 1 minute, immersed in pure water for 1 minute, finally took out the silicon wafer from pure water, and sprayed air to remove the surface. Pure water.

[Example 58]

Mixing trimethylchloromethane [(CH ₃ ) ₃ SiCl]: 3 g of hydrazine compound B, 2-propanol (iPA) as an organic solvent: 5 g, and a mixed solvent of HFE-7100: 92 g, as in the following formula In the reaction, a reaction liquid for forming a protective film containing trimethyl isopropoxide as the hydrazine compound A, hydrogen chloride as an acid, and HFE-7100 as an organic solvent was obtained, and all of them were the same as those in Example 1. the same. As a result of the evaluation, as shown in Table 3, the contact angle after the surface treatment was 68°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 1.2 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

(CH ₃ ) ₃ Si-Cl+(CH ₃ ) ₂ CH-OH → (CH ₃ ) ₃ Si-OCH(CH ₃ ) ₂ +H-Cl

[Examples 59 to 73]

The conditions of the concentration of the hydrazine compound B used in Example 58, the concentration of the alcohol, the concentration of the alcohol, and the organic solvent were changed, and the surface treatment of the wafer was carried out, and the evaluation was further carried out. The results are shown in Table 3.

In the table, "HFE-7100/iPA" means a mixed solvent of HFE-7100 and iPA, and the alcohol concentration in the starting material is 5% by mass. "CTFP/iPA" means a mixed solvent of CTFP and iPA, and the alcohol concentration in the starting material is set to 5% by mass. "DCTFP/iPA" means a mixed solvent of DCTFP and iPA, and the alcohol concentration in the starting material is set to 5% by mass. "nPA" means 1-propanol, and "HFE-7100/nPA" means a mixed solvent of HFE-7100 and nPA, and the alcohol concentration in the starting material is 5% by mass. "HFE-7100/ethanol" means a mixed solvent of HFE-7100 and ethanol, and the alcohol concentration in the starting material is 5% by mass. "PDO" means 1,2-pentanediol, and "HFE-7100/PDO" means a mixed solvent of HFE-7100 and PDO, and the alcohol concentration in the starting material is set to 5% by mass. "PGME" means propylene glycol monomethyl ether, and "HFE-7100/PGME" means a mixed solvent of HFE-7100 and PGME, and the alcohol concentration in the starting material is 5% by mass.

[Example 74]

The hydrazine compound B in the protective film forming chemical solution is reacted as shown in the following formula using dimethylchlorodecane [(CH ₃ ) ₂ Si(H)Cl], thereby obtaining a dimethyl group containing ruthenium compound A. All of the same procedures as in Example 60 were carried out except that the protective liquid for forming a protective film of propoxy decane was used. As a result of the evaluation, as shown in Table 3, the contact angle after the surface treatment was 80°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 0.6 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

(CH ₃ ) ₂ Si(H)-Cl+(CH ₃ ) ₂ CH-OH → (CH ₃ ) ₂ Si(H)-OCH(CH ₃ ) ₂ +H-Cl

[Examples 75 to 76]

The conditions such as the alcohol, the alcohol concentration, and the organic solvent used in Example 74 were changed, and the surface treatment of the wafer was carried out, and the evaluation was further performed. The results are shown in Table 3.

[Example 77]

With a polysilazane of the liquid silicon compound of the D-tetramethyldisiloxane as a protective film formed of silicon _{[(CH 3) 2 Si (} H) -NH-Si (H) (CH 3) 2]: 10g, as the organic solvent of 1-propanol (nPA): 5 g and HFE-7100: 85 g of a mixed solvent are mixed and reacted as shown in the following formula, thereby obtaining dimethylpropoxydecane as a hydrazine compound C, ammonia as a base, The chemical solution for forming a protective film of HFE-7100 as an organic solvent was the same as that of Example 75. As a result of the evaluation, as shown in Table 4, the contact angle after the surface treatment was 70°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 1.1 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

(CH ₃ ) ₂ Si(H)-NH-Si(H)(CH ₃ ) ₂ +2C ₃ H ₇ -OH → 2(CH ₃ ) ₂ Si(H)-OC ₃ H ₇ +NH ₃

[Example 78]

The ruthenium compound B in the protective film forming chemical solution is reacted as shown in the following formula using ethyl dimethyl chlorodecane [C ₂ H ₅ Si(CH ₃ ) ₂ Cl], thereby obtaining B which is a ruthenium compound A. All of the same procedures as in Example 60 were carried out except that the protective liquid for forming a protective film of dimethyl isopropyl isopropane was used. As a result of the evaluation, as shown in Table 4, the contact angle after the surface treatment was 74°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 0.9 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

C ₂ H ₅ Si(CH ₃ ) ₂ -Cl+(CH ₃ ) ₂ CH-OH → C ₂ H ₅ Si(CH ₃ ) ₂ -OCH(CH ₃ ) ₂ +H-Cl

[Examples 79 to 80]

The conditions such as the alcohol, the alcohol concentration, and the organic solvent used in Example 78 were changed, and the surface treatment of the wafer was carried out, and the evaluation was further performed. The results are shown in Table 4.

[Example 81]

The bismuth compound B in the protective film forming chemical solution is reacted as shown in the following formula using propyldimethylchlorochloromethane [C ₃ H ₇ Si(CH ₃ ) ₂ Cl], thereby obtaining C as a bismuth compound A. All of the same procedures as in Example 60 were carried out except that the protective liquid for forming a protective film of dimethyl isopropyl isopropane was used. As a result of the evaluation, as shown in Table 4, the contact angle after the surface treatment was 76°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 0.8 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

C ₃ H ₇ Si(CH ₃ ) ₂ -Cl+(CH ₃ ) ₂ CH-OH → C ₃ H ₇ Si(CH ₃ ) ₂ -OCH(CH ₃ ) ₂ +H-Cl

[Examples 82 to 83]

The conditions such as the alcohol, the alcohol concentration, and the organic solvent used in Example 81 were changed, and the surface treatment of the wafer was carried out, and the evaluation was further performed. The results are shown in Table 4.

[Example 84]

The bismuth compound B in the protective film forming chemical solution is a reaction product of the following formula, using trifluoropropyldimethylchlorodecane [CF ₃ C ₂ H ₄ Si(CH ₃ ) ₂ Cl], thereby obtaining inclusion as a hydrazine. The same procedure as in Example 60 except that the protective liquid for forming a protective film of trifluoropropyldimethyl isopropoxydecane of Compound A was used. As a result of the evaluation, as shown in Table 4, the contact angle after the surface treatment was 72°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 1.0 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

CF ₃ C ₂ H ₄ Si(CH ₃ ) ₂ -Cl+(CH ₃ ) ₂ CH-OH → CF ₃ C ₂ H ₄ Si(CH ₃ ) ₂ -OCH(CH ₃ ) ₂ +H-Cl

[Examples 85 to 86]

The conditions such as the alcohol, the alcohol concentration, and the organic solvent used in Example 84 were changed, and the surface treatment of the wafer was carried out, and the evaluation was further performed. The results are shown in Table 4.

[Example 87]

The ruthenium compound B in the protective film forming chemical solution is reacted as shown in the following formula using nonafluorohexyl dimethyl chlorodecane [CF ₃ (CF ₂ ) ₃ C ₂ H ₄ Si(CH ₃ ) ₂ Cl] The same procedure as in Example 60 was carried out except that a chemical solution for forming a protective film containing nonafluorohexyldimethyl isopropoxy decane as the hydrazine compound A was obtained. As a result of the evaluation, as shown in Table 4, the contact angle after the surface treatment was 70°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 1.1 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

CF ₃ (CF ₂ ) ₃ C ₂ H ₄ Si(CH ₃ ) ₂ -Cl+(CH ₃ ) ₂ CH-OH → CF ₃ (CF ₂ ) ₃ C ₂ H ₄ Si(CH ₃ ) ₂ - OCH(CH ₃ ) ₂ +H-Cl

[Examples 88 to 89]

The conditions such as the alcohol, the alcohol concentration, and the organic solvent used in Example 87 were changed, and the surface treatment of the wafer was carried out, and the evaluation was further performed. The results are shown in Table 4.

[Example 90]

The same procedure as in Example 88 was carried out, except that a smooth tantalum nitride film (Si wafer having a tantalum nitride layer having a thickness of 0.3 μm on the surface) was used. As a result of the evaluation, as shown in Table 4, the contact angle after the surface treatment was 70°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 1.1 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

[Example 91]

The same procedure as in Example 88 was carried out except that a wafer having no film on the surface was used. As a result of the evaluation, as shown in Table 4, the contact angle after the surface treatment was 70°, and the water repellency imparting effect was exhibited. Further, the capillary force at the time of holding water was 1.1 MN/m ² , and the capillary force was small. Further, since the contact angle after the UV irradiation is less than 10°, the protective film can be removed. Further, since the Ra value of the wafer after the UV irradiation was less than 0.5 nm, it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation.

[Comparative Example 1]

The same procedure as in the first embodiment was carried out except that the protective film forming chemical liquid was not supplied to the silicon wafer. That is, in this comparative example, the wafer in the surface state which was not water-repellent was evaluated. The evaluation results are shown in Table 5. The contact angle of the wafer was as low as 3°, and the capillary force when the water was held was 3.2 MN/m ² .

[Comparative Example 2]

Trimethyl methoxy decane: 3.0 g, iPA: 94.6 g were mixed, and then 1 N hydrochloric acid aqueous solution: 2.4 g was added, and the mixture was stirred at room temperature for about 24 hours to obtain a protective film forming chemical solution, and no moisture removal was performed. The same procedure as in Example 1 was carried out except that the purification was carried out. The amount of water in the obtained chemical solution for forming a protective film was 21,000 ppm by mass. The evaluation results are shown in Table 5. The contact angle after the surface treatment was as low as 16°, and the capillary force when the water was kept was 3.1 MN/m ² .

[Comparative Example 3]

In the preparation of the chemical solution for forming a protective film, the same as in Example 1 except that trimethylmethoxydecane was not added. That is, in this comparative example, the chemical liquid containing no hydrazine compound A was prepared. The evaluation results are shown in Table 5. The contact angle after the surface treatment was as low as 14°, and the capillary force when the water was kept was 3.1 MN/m ² .

[Comparative Example 4]

In the preparation of the chemical solution for forming a protective film, the same procedure as in Example 1 was carried out except that trifluoromethanesulfonic acid was not added. That is, in this comparative example, a chemical liquid containing no acid was prepared. The evaluation results are shown in Table 5. The contact angle after the surface treatment was as low as 10°, and the capillary force when the water was kept was 3.2 MN/m ² .

[Comparative Example 5]

The hexamethyldioxazane [(CH ₃ ) ₃ Si-NH-Si(CH ₃ ) ₃ ] as the hydrazine compound A in the protective film forming solution was used, and all but the examples were used. 14 is the same. The evaluation results are shown in Table 5, the contact angle after the surface treatment is as low as 30 °, the capillary force is larger when the water is kept 2.8 MN / m ^2.

[Comparative Example 6]

A medicinal solution for forming a protective film is obtained by using hexamethyldiazepine [(CH ₃ ) ₃ Si-NH-Si(CH ₃ ) ₃ ] as the hydrazine compound D in the protective solution forming liquid, and all but The same as in the example 77. The evaluation results are shown in Table 6. The contact angle after the surface treatment was as low as 40°, and the capillary force at the time of holding water was as large as 2.5 MN/m ² .

[Comparative Example 7]

In the same manner as in Example 4, except that 0.5 g of water was added to 100 g of the protective film-forming chemical solution obtained in Example 4, and the amount of water in the chemical solution was more than 5,000 ppm by mass. The contact angle after surface treatment was as low as 14°, and the capillary force when holding water was as large as 3.1 MN/m ² . The reason is considered to be that excessive water is present in the chemical solution to lower the effect as an acid catalyst.

1‧‧‧ wafer

2‧‧‧Micro-concave pattern on the surface of the wafer

3‧‧‧The convex part of the pattern

4‧‧‧The recess of the pattern

5‧‧‧Width of the recess

6‧‧‧ Height of the convex part

7‧‧‧Width of the convex part

8‧‧‧ Protective liquid for forming a protective film held in the recess 4

9‧‧‧Water-based cleaning solution held in the recess 4

10‧‧‧Protective film

1 is a schematic plan view showing a wafer 1 having a surface having a fine uneven pattern 2; FIG. 2 is a view showing a portion of a-a' cross section of FIG. 1, and FIG. 3 is a view showing a protective film for holding a protective film in the recess 4 by a cleaning step. FIG. 4 is a schematic view showing a state in which the chemical liquid 8 is formed; and FIG. 4 is a schematic view showing a state in which the aqueous cleaning liquid is held in the concave portion 4 in which the protective film is formed.

1‧‧‧ wafer

3‧‧‧The convex part of the pattern

4‧‧‧The recess of the pattern

9‧‧‧Water-based cleaning solution held in the recess 4

10‧‧‧Protective film

Claims (23)

A chemical solution for forming a water repellent protective film, which is characterized in that at least a recessed surface of the concave-convex pattern is used when the wafer having a fine uneven pattern on the surface and at least a part of the concave-convex pattern contains a germanium element is cleaned a chemical solution for forming a water repellent protective film, comprising an antimony compound A represented by the following formula [1], an acid which supplies protons to the antimony compound A or/and an acid which receives electrons from the antimony compound A, the above liquid solution The total amount of water in the medium is 1000 ppm by mass or less relative to the total amount of the liquid, and R ¹ _a Si(H) _b (X) _4-ab [1] (in the formula [1], R ¹ respectively Independently from each other, it is at least one selected from the group consisting of a monovalent organic group having a hydrocarbon group having 1 to 18 carbon atoms and a monovalent organic group having a fluoroalkyl chain having 1 to 8 carbon atoms, and X is independently selected from each other. The halogen group and the element bonded to the Si element are at least one of oxygen or nitrogen monovalent organic groups and nitrile groups, a is an integer of 1 to 3, b is an integer of 0 to 2, and the total of a and b is 3 or less), in which the particles in the liquid phase in the above liquid solution are measured by a particle detector in a light scattering type liquid, the number of particles larger than 0.5 μm is per 1 The amount of the solution in the mL is 100 or less. The aqueous solution for forming a water repellent protective film according to claim 1, wherein the hydrazine compound A represented by the above formula [1] is an alkoxy decane represented by the following formula [2], [Chem. 23] R ² _c Si (H) _d (OR ³ ) _4-cd [2] (In the formula [2], R ^{2 is} each independently selected from a hydrocarbon group having a hydrocarbon group having 1 to 18 carbon atoms and a carbon number of 1 At least one of the one-valent organic groups of the fluoroalkyl chain of ~8, and R ³ are each independently at least one selected from the group consisting of a part or all of the hydrogen element which may be substituted by a fluorine element and having at least one carbon number of 1 to 18 carbon atoms. Further, the hydrocarbon group represented by R ³ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group; c is an integer of 1 to 3, d is an integer of 0 to 2, and a total of c and d It is 3 or less). The aqueous solution for forming a water repellent protective film according to claim 2, wherein the alkoxydecane and the acid contained in the chemical solution are obtained by reacting the hydrazine compound B and the alcohol represented by the formula [3]. 24] R ⁴ _e Si(H) _f (Y) _4-ef +(4-ef)R ⁵ -OH → R ⁴ _e Si(H) _f (OR ⁵ ) _4-ef +(4-ef)HY [ 3] (In the formula [3], R ⁴ _e Si(H) _f (Y) _4-ef represents an anthracene compound B, R ⁵ -OH represents an alcohol, and R ⁴ _e Si(H) _f (OR ⁵ ) _{4- Ef} represents an alkoxydecane obtained by the reaction, and HY represents an acid; and R ^{4 is} each independently selected from a monovalent organic group having a hydrocarbon group having 1 to 18 carbon atoms and a fluoroalkyl group having 1 to 8 carbon atoms. one chain monovalent organic group at least one group, R ⁵ are each independently selected from hydrogen elements may be partially or entirely substituted by fluorine element of carbon atoms of at least one of the one group having 1 to 18 monovalent hydrocarbon group; Furthermore, The hydrocarbon group represented by R ⁵ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group; e is an integer of 1 to 3, f is an integer of 0 to 2, and a total of e and f is 3 or less; Y each independently represents a group selected from halo, -OS (O ₂₎ -R ⁶ and ^{-OC (O) -R 6 (R} 6 part or all of the hydrogen-based elements may be replaced by fluorine element At least one hydrocarbon group having a carbon number of 1 to 8) in). A chemical solution for forming a water repellent protective film, which is characterized in that when a wafer having a fine concavo-convex pattern on its surface and at least a part of the concavo-convex pattern contains a germanium element is cleaned, it is formed on at least the concave surface of the concavo-convex pattern. The chemical solution of the water repellent protective film comprises a hydrazine compound C represented by the following formula [4] and a base having a water content of 35% by mass or less, and the total amount of water in the medicinal solution is relative to the total amount of the medicinal solution. 1000 mass ppm or less, [ _Chem . 25] R ⁷ _g Si(H) _h (CH ₃ ) _w (Z) _4-ghw [4] (In the formula [4], R ^{7 is} independently selected from the carbon number It is at least one of a monovalent organic group of a hydrocarbon group of 2 to 18 and a monovalent organic group of a fluoroalkyl chain having 2 to 8 carbon atoms, and Z is independently selected from a halogen group and bonded to a Si element. The element is at least one group of one of the oxygen organic groups, g is an integer of 0 to 3, h is an integer of 0 to 2, w is an integer of 0 to 2, and the total of g and h is 1 to 3, g The sum of w and 1 is 3 to 3, and the total of g, h, and w is 1 to 3), wherein the liquid phase in the liquid phase in the above liquid is more than 0.5 μm when measured by a particle detector in a liquid scattering type liquid particle detector. Number of particles The amount is 100 or less per 1 mL of the drug solution. The aqueous solution for forming a water repellent protective film according to claim 4, wherein the oxime compound C represented by the above formula [4] is an alkoxy decane represented by the following formula [5], [Chem. 26] R ⁸ _i Si (H) _j (CH ₃ ) _k (OR ⁹ ) _4-ijk [5] (In the formula [5], R ^{8 is} each independently selected from a hydrocarbon group having a hydrocarbon group having 2 to 18 carbon atoms and The at least one group of the one-valent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, and R ⁹ are each independently selected from a part or all of hydrogen elements which may be substituted by a fluorine element and have a carbon number of 1 to 18 At least one group of the valent hydrocarbon group; further, the hydrocarbon group represented by R ⁹ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group; i is an integer of 0 to 3, and j is an integer of 0 to 2, k is an integer from 0 to 2, the total of i and j is 1 to 3, the total of i and k is 1 to 3, and the total of i, j and k is 1 to 3). The aqueous solution for forming a water-repellent protective film according to claim 5, wherein the alkoxydecane and the base contained in the above-mentioned chemical liquid are obtained by reacting the hydrazine compound D represented by the formula [6] or the formula [7] with an alcohol. , [Chem. 27] R ¹⁰ _p Si(H) _q (CH ₃ ) _r (W) _4-pqr +(4-pqr)R ¹¹ -OH → R ¹⁰ _p Si(H) _q (CH ₃ ) _r ( OR ¹¹ ) _4-pqr +(4-pqr)HW [6] [R ¹² _s (CH ₃ ) _t (H) _u Si] _v NR ¹³ _3-v +v R ¹⁴ -OH → v R ¹² _s (CH ₃ ) _t (H) _u SiOR ¹⁴ +N(H) _v (R ¹³ ) _3-v [7] (in the formula [6], R ¹⁰ _p Si(H) _q (CH ₃ ) _r (W) _{4 -pqr} represents _hydrazine compound D, R ¹¹ -OH represents an alcohol, R ¹⁰ _p Si(H) _q (CH ₃ ) _r (OR ¹¹ ) _4-pqr represents an alkoxy decane obtained by the reaction, and HW represents a base; In the formula [7], [R ¹² _s (CH ₃ ) _t (H) _u Si] _v NR ¹³ _3-v represents an indole compound D, R ¹⁴ -OH represents an alcohol, R ¹² _s (CH ₃ ) _t ( H) _u SiOR ¹⁴ represents an alkoxydecane obtained by the reaction, and N(H) _v (R ¹³ ) _3-v represents a base; and R ^{10 is} independently of each other and is selected from one of hydrocarbon groups having a carbon number of 2 to 18. a valence organic group and at least one group of a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, and R ¹¹ are each independently selected from the group consisting of The partial or total hydrogen element may be substituted with a fluorine element and the carbon number is at least one of 1 to 18 one-valent hydrocarbon groups; further, the hydrocarbon group represented by R ¹¹ may further comprise a carbonyl group, an ether bond, an ester bond, or a hydroxyl group. One or more; R ^{12 is} independently selected from at least one selected from the group consisting of a monovalent organic group having a hydrocarbon group having 2 to 18 carbon atoms and a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, R ^{13 is} independently selected from at least one group selected from the group consisting of a monovalent organic group having 1 to 8 carbon atoms and hydrogen, and each of R ^{14 is} independently selected from a part or all of hydrogen. The number of carbon atoms which may be substituted by fluorine is 1~ And a hydrocarbon group represented by R ¹⁴ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group; p is an integer of 0 to 3, and q is 0 to 2; The integer, r is an integer from 0 to 2, the total of p and q is 1 to 3, the sum of p and r is 1 to 3, the total of p, q and r is 1 to 3, and s is an integer of 0 to 3. , t is an integer from 0 to 2, u is an integer from 0 to 2, and the total of s, t, and u is 3, and v is an integer from 1 to 3. Further, W is independently selected from the group consisting of an amine group and a dialkyl group. At least one of an amino group and an isocyanate group). The aqueous solution for forming a water repellent protective film according to any one of claims 1 to 6, wherein a metal impurity content of each of elements of Na, Mg, K, Ca, Mn, Fe, and Cu in the chemical solution is relative to the liquid solution The total amount is 100 mass ppb or less. The aqueous solution for forming a water repellent protective film according to any one of claims 1 to 6, wherein a metal impurity content of each of elements of Na, Mg, K, Ca, Mn, Fe, and Cu in the chemical solution is relative to the liquid solution The total amount is 100 mass ppb or less. A modulation method, which is a method for modulating a water repellent protective film forming liquid according to any one of the claims 1, the request item 2, the request item 4, the request item 5, the request item 7 and the request item 8, And removing at least one of moisture, particles, and metal impurities with respect to at least one of ruthenium compound A or ruthenium compound C, an acid or a base, and a mixed liquid mixture before mixing as a raw material of the protective film forming chemical solution. . A modulation method characterized in that it is as claimed in claim 3, and a request item (6) The method for preparing a water-repellent protective film-forming chemical solution according to any one of the preceding claims, wherein the ruthenium compound B or the ruthenium compound D and the alcohol before mixing are used as a raw material of the protective film forming chemical solution At least one of the mixed liquid mixture removes at least one of moisture, particles, and metal impurities. A cleaning method for cleaning a wafer surface having a fine concavo-convex pattern on a surface by using the protective film forming liquid solution according to any one of claims 1 to 8, the method comprising the surface of the wafer The step of removing the protective film from the surface of the wafer after removing the cleaning solution. The cleaning method of claim 11, wherein the step of removing the protective film from the surface of the wafer is selected from the steps of performing light irradiation on the surface of the wafer, processing of heating the wafer, processing of ozone exposure on the wafer, and At least one of the processes of plasma irradiation of the wafer surface. A chemical solution for forming a water repellent protective film, which is characterized in that at least a recessed surface of the concave-convex pattern is used when the wafer having a fine uneven pattern on the surface and at least a part of the concave-convex pattern contains a germanium element is cleaned a chemical solution for forming a water repellent protective film, comprising an antimony compound A represented by the following formula [1], an acid which supplies protons to the antimony compound A or/and an acid which receives electrons from the antimony compound A, the above liquid solution The total amount of water in the medium is 1000 ppm by mass or less relative to the total amount of the liquid, and R ¹ _a Si(H) _b (X) _4-ab [1] (in the formula [1], R ¹ respectively Independently from each other, it is at least one selected from the group consisting of a monovalent organic group having a hydrocarbon group having 1 to 18 carbon atoms and a monovalent organic group having a fluoroalkyl chain having 1 to 8 carbon atoms, and X is independently selected from each other. The halogen group and the element bonded to the Si element are at least one of oxygen or nitrogen monovalent organic groups and nitrile groups, a is an integer of 1 to 3, b is an integer of 0 to 2, and the total of a and b is 3 or less), wherein the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the above liquid is 100 mass ppb with respect to the total amount of the liquid solution, respectively the following. The requested item 13 of the water repellent protective film forming liquid, wherein the silicon of the above formula [1] A compound represented by the following general formula [2] shown in the alkoxy Silane, [Formula 23] R ² _c Si (H) _d (OR ³ ) _4-cd [2] (In the formula [2], R ^{2 is} each independently selected from a hydrocarbon group having a hydrocarbon group having 1 to 18 carbon atoms and a carbon number of 1 At least one of the one-valent organic groups of the fluoroalkyl chain of ~8, and R ³ are each independently at least one selected from the group consisting of a part or all of the hydrogen element which may be substituted by a fluorine element and having at least one carbon number of 1 to 18 carbon atoms. Further, the hydrocarbon group represented by R ³ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group; c is an integer of 1 to 3, d is an integer of 0 to 2, and a total of c and d It is 3 or less). The aqueous solution for forming a water repellent protective film according to claim 14, wherein the alkoxydecane and the acid contained in the chemical solution are obtained by reacting the hydrazine compound B and the alcohol represented by the formula [3]. 24] R ⁴ _e Si(H) _f (Y) _4-ef +(4-ef)R ⁵ -OH → R ⁴ _e Si(H) _f (OR ⁵ ) _4-ef +(4-ef)HY [ 3] (In the formula [3], R ⁴ _e Si(H) _f (Y) _4-ef represents an anthracene compound B, R ⁵ -OH represents an alcohol, and R ⁴ _e Si(H) _f (OR ⁵ ) _{4- Ef} represents an alkoxydecane obtained by the reaction, and HY represents an acid; and R ^{4 is} each independently selected from a monovalent organic group having a hydrocarbon group having 1 to 18 carbon atoms and a fluoroalkyl group having 1 to 8 carbon atoms. At least one group of one of the chain organic groups, R ⁵ being independently of each other is at least one selected from the group consisting of a part or all of hydrogen elements which may be substituted by a fluorine element and having a carbon number of 1 to 18 one-valent hydrocarbon groups; The hydrocarbon group represented by R ⁵ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group; e is an integer of 1 to 3, f is an integer of 0 to 2, and a total of e and f is 3 or less; Y each independently represents a group selected from halo, -OS (O ₂₎ -R ⁶ and ^{-OC (O) -R 6 (R} 6 part or all of the hydrogen-based elements may be replaced by fluorine element At least one hydrocarbon group having a carbon number of 1 to 8) in). A chemical solution for forming a water repellent protective film, which is characterized in that when a wafer having a fine concavo-convex pattern on its surface and at least a part of the concavo-convex pattern contains a germanium element is cleaned, it is formed on at least the concave surface of the concavo-convex pattern. The chemical solution of the water repellent protective film comprises a hydrazine compound C represented by the following formula [4] and a base having a water content of 35% by mass or less, and the total amount of water in the medicinal solution is relative to the total amount of the medicinal solution. 1000 ppm ppm or less, [ _Chem . 25] R ⁷ _g Si(H) _h (CH ₃ ) _w (z) _4-ghw [4] (In the formula [4], R ^{7 is} independently selected from the carbon number It is at least one of a monovalent organic group of a hydrocarbon group of 2 to 18 and a monovalent organic group of a fluoroalkyl chain having 2 to 8 carbon atoms, and Z is independently selected from a halogen group and bonded to a Si element. The element is at least one group of one of the oxygen organic groups, g is an integer of 0 to 3, h is an integer of 0 to 2, w is an integer of 0 to 2, and the total of g and h is 1 to 3, g The sum of w and 1 is 3 to 3, and the total of g, h, and w is 1 to 3), wherein the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the above liquid is relative to The total amount of the liquid is 10 0 mass ppb or less. The aqueous solution for forming a water repellent protective film according to claim 16, wherein the hydrazine compound C represented by the above formula [4] is an alkoxy decane represented by the following formula [5], [Chem. 26] R ⁸ _i Si (H) _j (CH ₃ ) _k (OR ⁹ ) _4-ijk [5] (In the formula [5], R ^{8 is} each independently selected from a hydrocarbon group having a hydrocarbon group having 2 to 18 carbon atoms and The at least one group of the one-valent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, and R ⁹ are each independently selected from a part or all of hydrogen elements which may be substituted by a fluorine element and have a carbon number of 1 to 18 At least one group of the valent hydrocarbon group; further, the hydrocarbon group represented by R ⁹ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group; i is an integer of 0 to 3, and j is an integer of 0 to 2, k is an integer from 0 to 2, the total of i and j is 1 to 3, the total of i and k is 1 to 3, and the total of i, j and k is 1 to 3). The aqueous solution for forming a water-repellent protective film according to claim 17, wherein the alkoxydecane and the base contained in the above-mentioned chemical solution are obtained by reacting the hydrazine compound D represented by the formula [6] or the formula [7] with an alcohol. , [Chem. 27] R ¹⁰ _p Si(H) _q (CH ₃ ) _r (W) _4-pqr +(4-pqr)R ¹¹ -OH → R ¹⁰ _p Si(H) _q (CH ₃ ) _r ( OR ¹¹ ) _4-pqr +(4-pqr)HW [6] [R ¹² _s (CH ₃ ) _t (H) _u Si] _v NR ¹³ _3-v +v R ¹⁴ -OH → v R ¹² _s (CH ₃ ) _t (H) _u SiOR ¹⁴ +N(H) _v (R ¹³ ) _3-v [7] (in the formula [6], R ¹⁰ _p Si(H) _q (CH ₃ ) _r (W) _{4 -pqr} represents _hydrazine compound D, R ¹¹ -OH represents an alcohol, R ¹⁰ _p Si(H) _q (CH ₃ ) _r (OR ¹¹ ) _4-pqr represents an alkoxy decane obtained by the reaction, and HW represents a base; In the formula [7], [R ¹² _s (CH ₃ ) _t (H) _u Si] _v NR ¹³ _3-v represents an indole compound D, R ¹⁴ -OH represents an alcohol, R ¹² _s (CH ₃ ) _t ( H) _u SiOR ¹⁴ represents an alkoxydecane obtained by the reaction, and N(H) _v (R ¹³ ) _3-v represents a base; and R ^{10 is} independently of each other and is selected from one of hydrocarbon groups having a carbon number of 2 to 18. and a monovalent organic group having a carbon number of 2 to 8 chain fluoroalkyl group at least one group of one of the monovalent organic group, R ¹¹ are each independently selected from Or all of the hydrogen elements may be substituted with one fluorine element having a carbon number of 1 to 18 is at least one monovalent hydrocarbon group; Moreover, the hydrocarbon group represented by R ¹¹ may contain a carbonyl group, an ether bond, an ester bond, hydroxyl group of One or more; R ^{12 is} independently selected from at least one selected from the group consisting of a monovalent organic group having a hydrocarbon group having 2 to 18 carbon atoms and a monovalent organic group having a fluoroalkyl chain having 2 to 8 carbon atoms, R ^{13 is} independently selected from at least one group selected from the group consisting of a monovalent organic group having 1 to 8 carbon atoms and hydrogen, and each of R ^{14 is} independently selected from a part or all of hydrogen. The number of carbon atoms which may be substituted by fluorine is 1~ And a hydrocarbon group represented by R ¹⁴ may further contain one or more of a carbonyl group, an ether bond, an ester bond, and a hydroxyl group; p is an integer of 0 to 3, and q is 0 to 2; The integer, r is an integer from 0 to 2, the total of p and q is 1 to 3, the sum of p and r is 1 to 3, the total of p, q and r is 1 to 3, and s is an integer of 0 to 3. , t is an integer from 0 to 2, u is an integer from 0 to 2, and the total of s, t, and u is 3, and v is an integer from 1 to 3. Further, W is independently selected from the group consisting of an amine group and a dialkyl group. At least one of an amino group and an isocyanate group) The aqueous solution for forming a water repellent protective film according to any one of claims 13 to 18, wherein, in the liquid phase in the liquid chemical, the particle is measured by a particle detector in a light scattering type liquid, the number of particles larger than 0.5 μm is Every 1mL of this There are 100 or less in the drug solution. A modulation method, which is a method for preparing a liquid repellency protective film forming solution according to any one of the claims 13, the request item 14, the request item 16, the request item 17, and the request item 19, and At least one of hydrazine compound A or hydrazine compound C, an acid or a base, and a mixed liquid mixture before mixing of the raw material for forming a protective film forming liquid, at least one of water, particles and metal impurities is removed. A method of preparing a chemical solution for forming a water repellent protective film according to any one of the claims 15 and 18, and as a raw material for the protective liquid for forming a protective film. At least one of hydrazine compound B or hydrazine compound D, an alcohol, and a mixed mixture before mixing, at least one of moisture, particles, and metal impurities is removed. A cleaning method for cleaning a wafer surface having a fine concavo-convex pattern on a surface by using the protective film forming liquid solution according to any one of claims 13 to 19, the method comprising the self-wafer surface The step of removing the protective film from the surface of the wafer after removing the cleaning solution. The cleaning method of claim 22, wherein the step of removing the protective film from the surface of the wafer is selected from the steps of performing light irradiation on the surface of the wafer, processing the heated wafer, performing ozone exposure on the wafer, and At least one of the processes of plasma irradiation of the wafer surface.